Fluoroalkenyl derivative and liquid crystal composition

ABSTRACT

The present invention is to provide liquid crystalline compounds having a wide temperature range of a liquid crystal phase, low viscosity, and large ratio of elastic constants; liquid crystal compositions comprising the compound; and liquid crystal display devices comprising the composition; the liquid crystalline compounds being fluoroalkenyl derivatives expressed by the general formula (1) ##STR1## wherein A 1 , A 2 , A 3 , and A 4  independently represent trans-1,4-cyclohexylene group or 1,4-phenylene group; Z 1 , Z 2 , and Z 3  independently represent --(CH 2 ) 2  --, --CH═CH--, --C≡C--, or a single bond; Q represents H or F; l is an integer of 1 to 5; m, n, and o are independently an integer of 0 to 5; p and q are independently an integer of 0 or 1; and each element which constitutes the derivatives may be an isotope of the element.

This application is a 371 application of International Application No.PCT/JP96/02950 filed Oct. 11, 1996.

TECHNICAL FIELD

The present invention relates to liquid crystalline compounds and liquidcrystal compositions. More specifically, it relates to novel liquidcrystalline compounds having a fluorine substituted alkenyl group at anend and having a fluorine substituted or unsubstituted alkenyl group atthe other end of the molecule; relates to liquid crystal compositionscomprising the compound; and relates to liquid crystal display devicescomprising the composition.

BACKGROUND ART

Display devices comprising liquid crystalline compounds have widely beenemployed for the displays of watches, tabletop calculators, wordprocessors, TV sets, or the likes. These display devices employ theoptical anisotropy and dielectric anisotropy of liquid crystallinecompounds.

Liquid crystal phase exists between a solid phase and a liquid phase,and the liquid crystal phase includes a nematic phase, smectic phase,and cholesteric phase as its specific form. Among which, the nematicphase is most in use at present for display devices. As the specifictype of display mode, TN (twisted nematic) mode, DS (dynamic scattering)mode, GH (guest-host) mode, DAP (deformation of aligned phases) mode allof which exhibit electro-optic effects have been developed. Meanwhile,display of liquid crystals in color is further progressing lately, andparticularly devices of TFT (thin-film-transistor) mode and STN (supertwisted nematic) mode both of which form a class of TN mode have nowbecome a main current.

Whereas many liquid crystalline compounds including ones which arecurrently at a stage of research are known up to now, compounds whichcan be filled in display devices as a single compound to actually use asliquid crystal composition have not been developed. This is becausewhereas liquid crystalline compounds expected to be used as a materialfor display devices must exhibit a liquid crystal phase at roomtemperature, at which display devices are most often used, as well as ina temperature range as wide as possible with the room temperature beingits center; must be sufficiently stable against environmental factorsunder conditions in which the devices are used; and must have physicalproperties sufficient to drive display devices, no compounds which cansatisfy these requirements by a single compound have been found.Accordingly, it is an actual circumstance at present that several kindor several tens kind of liquid crystalline compounds, and nonliquid-crystalline compounds when necessary, are mixed to prepare liquidcrystal compositions having the required characteristics. It isconsidered to be necessary that these liquid crystal compositions arestable against moisture, light, heat, and air which are usually presentunder the conditions in which display devices are used; are stable alsoagainst electric field and electromagnetic radiation; and are chemicallystable against liquid crystalline compounds to be mixed. Also, it isconsidered to be necessary that liquid crystal compositions have anappropriate value of physical properties such as optical anisotropy(Δn), dielectric anisotropy (Δε), viscosity (η), electroconductivity,and ratio of elastic constants (K₃₃ /K₁₁ ; K₃₃ : bend elastic constant,K₁₁ : splay elastic constant) depending on the display modes and theshape of display devices. Further, it is important that each componentin liquid crystal compositions have a good mutual solubility to oneanother.

It is considered to be necessary that the liquid crystal compounds usedin displays of STN mode particularly have a low viscosity, large K₃₃/K₁₁, and wide temperature range of a liquid crystal phase in additionto the properties described above. Further, a low threshold voltage(Vth) is quite recently considered to be necessary accompanied withdriving of display devices at a low voltage.

That is, low viscosity is an essential property for achieving a highspeed response. Also, large K₃₃ /K₁₁ makes the change of transmittancearound V_(th) steep and makes the production of display devices of ahigh contrast possible. As the compounds exhibiting a large K₃₃ /K₁₁,ones having an alkenyl group as a lateral chain, for example, compoundsexpressed by the formula (a) disclosed in Japanese patent publicationNo. Hei 4-30382 and compounds expressed by the formula (b) disclosed inJapanese patent publication No. Hei 7-2653 are already known. However,since these compounds have a strong tendency to develop a smectic phaseby themselves, they sometimes separate crystals or develop a smecticphase particularly at low temperatures when used as a component ofliquid crystal compositions. Thus, the compounds can not be said to begood in mutual solubility at low temperatures.

Besides, whereas these compounds exhibit some extent of viscosityreducing effect on liquid crystal compositions to which the compoundsare mixed, the compounds have a defect of lowering clearing point, andhave a problem that they remarkably lower Δε when added to liquidcrystal compositions having a high Δε used for the purpose of drivingthe devices at low voltages, since the compounds themselves have aremarkably low Δε.

As compounds having a structure similar to that of the compounds of thepresent invention, ones expressed by the formula (c) are known as shownin U.S. Pat. No. 5,183,587. However, these compounds have a problem thatheat stability is very poor. ##STR2##

In addition, compounds having only an alkenyl group or a halogensubstituted alkenyl group as a terminal group in the molecule aredisclosed, for example, in Laid-open Japanese Patent Publication Nos.Sho 61-83136 and Sho 63-142091. However, these compounds areinsufficient for collectively achieving the effect of maintaining orraising clearing point and the effect of not lowering Δε (not raisingV_(th)) of liquid crystal compositions. Besides, these compounds have adefect in solubility to other known liquid crystal compounds,particularly in that at low temperatures.

From such circumstances in conventional technology, development ofliquid crystalline compounds having a low viscosity, large K₃₃ /K₁₁,excellent heat stability, wide temperature range of a liquid crystalphase, comparatively low V_(th), and improved solubility at lowtemperatures has been desired.

DISCLOSURE OF THE INVENTION

An object of the present invention is to solve the defects inconventional technology described above. Another object of the presentinvention is to provide liquid crystalline compounds having a lowviscosity, large K₃₃ /K₁₁, excellent heat stability, wide temperaturerange of a liquid crystal phase, and improved solubility at lowtemperatures in particular; to provide liquid crystal compositionscomprising the compound; and to provide liquid crystal display devicescomprising the composition.

The present invention for achieving the objects described are summarizedas follows:

(1) A fluoroalkenyl derivative expressed by the general formula (1)##STR3## wherein A₁, A₂, A₃, and A₄ independently representtrans-1,4-cyclohexylene group or 1,4-phenylene group at least onehydrogen atom of which six-membered ring may be replaced by a halogenatom; Z₁, Z₂, and Z₃ independently represent --(CH₂)₂ --, --CH═CH--,--C≡C--, or a single bond; Q represents H or F; l is an integer of 1 to5; m, n, and o are independently an integer of 0 to 5; p and q areindependently an integer of 0 or 1; and each element which constitutesthe derivative may be an isotope of the element.

(2) The fluoroalkenyl derivative recited in paragraph (1) above whereinZ₃ represents a single bond; both A₃ and A₄ representtrans-1,4-cyclohexylene group; and both p and q are 0.

(3) The fluoroalkenyl derivative recited in paragraph (1) above whereinboth Z₂ and Z₃ represent a single bond; A₂, A₃, and A₄ representtrans-1,4-cyclohexylene group; p is 0; and q is 1.

(4) The fluoroalkenyl derivative recited in paragraph (1) above whereinboth Z₂ and Z₃ represent a single bond; both A₂ and A₄ representtrans-1,4-cyclohexylene group; A₃ represents 1,4-phenylene group; p is0; and q is 1.

(5) The fluoroalkenyl derivative recited in paragraph (1) above whereinZ₁, Z₂, and Z₃ represent a single bond; both A₁ and A₄ representtrans-1,4-cyclohexylene group; both A₂ and A₃ represent 1,4-phenylenegroup; and both p and q are 1.

(6) A liquid crystal composition comprising at least 2 components andcomprising at least one fluoroalkenyl derivative recited in any one ofparagraphs (1) to (5) above.

(7) A liquid crystal composition comprising, as a first component, atleast one fluoroalkenyl derivative recited in any one of paragraphs (1)to (5) above, and comprising, as a second component, at least onecompound selected from the group consisting of the compounds expressedby any one of the general formulas (2), (3), and (4) ##STR4## wherein R₁represents an alkyl group having 1 to 10 carbon atoms; X₁ represents F,Cl, OCF₃, OCF₂ H, CF₃, CF₂ H, or CFH₂ ; L₁, L₂, L₃, and L₄ independentlyrepresent H or F; Z₄ and Z₅ independently represent --(CH₂)₂ --,--CH═CH--, or a single bond; and a is 1 or 2.

(8) A liquid crystal composition comprising, as a first component, atleast one fluoroalkenyl derivative recited in any one of paragraphs (1)to (5) above, and comprising, as a second component, at least onecompound selected from the group consisting of the compounds expressedby any one of the general formulas (5), (6), (7), (8), and (9) ##STR5##wherein R₂ represents F, an alkyl group having 1 to 10 carbon atoms, oran alkenyl group having 2 to 10 carbon atoms, in which alkyl group oralkenyl group one or more non-adjacent methylene groups (--CH₂ --) mayeach be replaced by an oxygen atom (--O--); ring A representstrans-1,4-cyclohexylene group, 1,4-phenylene group, pyrimidine-2,5-diylgroup, or 1,3-dioxane-2,5-diyl group; ring B representstrans-1,4-cyclohexylene group, 1,4-phenylene group, orpyrimidine-2,5-diyl group; ring C represents trans-1,4-cyclohexylenegroup or 1,4-phenylene group; Z₆ represents --(CH₂)₂ --, --COO--, or asingle bond; L₅ and L₆ independently represent H or F; and b and c areindependently 0 or 1, ##STR6## wherein R₃ represents an alkyl grouphaving 1 to 10 carbon atoms; L₇ represents H or F; and d is 0 or 1,##STR7## wherein R₄ represents an alkyl group having 1 to 10 carbonatoms; ring D and ring E independently represent trans-1,4-cyclohexylenegroup or 1,4-phenylene group; Z₇ and Z₈ independently represent --COO--or a single bond; Z₉ represents --COO-- or --C≡C--; L₈ and L₉independently represent H or F; X₂ represents F, OCF₃, OCF₂ H, CF₃, CF₂H, or CFH₂ ; and e, f, and g are independently 0 or 1, ##STR8## whereinR₅ and R₆ independently represent an alkyl group having 1 to 10 carbonatoms or an alkenyl group having 2 to 10 carbon atoms, in which alkyl oralkenyl group one or more non-adjacent methylene groups (--CH₂ --) mayeach be replaced by an oxygen atom (--O--); ring G representstrans-1,4-cyclohexylene group, 1,4-phenylene group, orpyrimidine-2,5-diyl group; ring H represents trans-1,4-cyclohexylenegroup or 1,4-phenylene group; Z₁₀ represents --C≡C--, --COO--, --(CH₂)₂--, --CH═CH--C≡C--, or a single bond; and Z₁₁ represents --COO-- or acovalent bond, ##STR9## wherein R₇ and R₈ independently represent analkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to10 carbon atoms, in which alkyl or alkenyl group one or morenon-adjacent methylene groups (--CH₂ --) may each be replaced by anoxygen atom (--O--) ring I represents trans-1,4-cyclohexylene group,1,4-phenylene group, or pyrimidine-2,5-diyl group; ring J representstrans-1,4-cyclohexylene group, 1,4-phenylene group at least one hydrogenatom on which ring may be replaced by F, or pyrimidine-2,5-diyl group;ring K represents trans-1,4-cyclohexylene group or 1,4-phenylene group ;Z₁₂ and Z₁₄ independently represent --COO--, --(CH₂)₂ --, or a singlebond; Z₁₃ represents --CH═CH--, --C≡C--, --COO--, or a single bond; andh is 0 or 1.

(9) A liquid crystal composition comprising, as a first component, atleast one fluoroalkenyl derivative recited in any one of paragraphs (1)to (5) above, comprising, as a part of a second component, at least onecompound selected from the group consisting of the compounds expressedby any one of the general formulas (2), (3), and (4); and comprising, asother part of the second component, at least one compound selected fromthe group consisting of the compounds expressed by any one of thegeneral formulas (5), (6), (7), (8), and (9).

(10) A liquid crystal display device comprising a liquid crystalcomposition recited in any one of paragraphs (6) to (9) above.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a chart showing a nuclear magnetic resonance spectrumindicating the structure of a compound of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Compounds of the present invention expressed by the general formula (1)are ones of two- to four-ring system compounds and are principallycharacterized by having a specific structure formed by introducing analkenyl group replaced by fluorine atom in one end and also introducingan alkenyl group in the other end of the molecule.

While these compounds of the present invention are applied as acomponent of liquid crystal compositions for display devices, thecompounds are extremely stable physically and chemically underconditions in which the display devices are used. Besides, the compoundshave a good solubility in liquid crystal compositions even at lowtemperatures and exhibit a wide temperature range of a nematic phase,low viscosity, medium degree of Δε, and large K₃₃ /K₁₁. Further, it ispossible to optionally adjust desired physical properties by properlyselecting a ring structure, bonding group, and structure of a lateralchain from the molecule constituting elements.

Accordingly, properties of liquid crystal compositions can be improvedas described in 1) to 4) below by using the compound of the presentinvention. Thus, it is possible to provide liquid crystal displaydevices which are stable against external environment and which furthermake a high speed response, high contrast, and driving at a low voltagepossible, by improving the properties of liquid crystal compositions.Particularly for TFT mode, liquid crystal display devices improved evenin the steepness and viewing angle can be provided through theimprovement of the properties of the compositions.

1) Viscosity can be reduced while maintaining or raising clearing point.

2) Δε is maintained and V_(th) is kept from raising.

3) Stabilized nematic liquid crystal compositions which do not separatecrystals or do not develop a smectic phase even at extremely lowtemperatures can be produced.

4) K₃₃ /K₁₁ can be increased.

Excellent properties of the compounds of the present invention describedabove are considered to be caused by a synergistic effect of a fluorinesubstituted or unsubstituted alkenyl group at one end and an alkenylgroup always substituted by fluorine atom at the other end of themolecule.

While any compounds of the present invention expressed by the generalformula (1) exhibit preferable properties as described above, they canbe made to a component for liquid crystal compositions complied withtheir purposes by selecting a proper group or numeral for A₁, A₂, A₃,A₄, Z₁ Z₂, Z₃, l, m, n, o, p, and q in the general formula (1).

For instance, particularly for producing liquid crystal compositions ofwhich the temperature of developing a liquid crystal phase desirablyshifts to higher temperature side, it is sufficient to select compoundsof four-ring system wherein p and q are 1, and for other end uses, it issufficient to select compounds of two- or three-ring system. Also, forliquid crystal compositions desirably having a high Δε, it is sufficientto use compounds in which one or two fluorine atoms are substituted forhydrogen atoms on 1,4-phenylene group in the molecule so that theirdipole moment faces the same direction as that of the dipole moment ofthe alkenyl group in which a fluorine atom is substituted, and suchcompositions exhibit even excellent solubility at low temperatures.

Improvement in optical anisotropy (Δn) can be adjusted by selecting aproper group and numeral for the A₁, A₂, A₃, A₄, Z₁, Z₂, Z₃, p, and q.For instance, for producing liquid crystal compositions desirably havinga high Δn, it is sufficient to use a compound having many 1,4-phenylenegroups and having single bond as each of Z₁, Z₂, and Z₃. Conversely forliquid crystal compositions desirably having a small Δn, it issufficient to use a compound having many trans-1,4-cyclohexylene groups.

Now, assuming that R₉ represents groups expressed by the followingformula (d), R₁₀ represents groups expressed by the following formula(e), ##STR10## Cyc represents trans-1,4-cyclohexylene group, Pherepresents 1,4-phenylene group at least one hydrogen atom on thesix-membered ring may be replaced by a halogen atom, the compounds ofthe present invention expressed by the general formula (1) can beclassified as follows:

Compounds having two six-membered rings:

    R.sub.9 -A.sub.3 -A.sub.4 -R.sub.10                        (1a)

    R.sub.9 -A.sub.3 -Z.sub.3 -A.sub.4 -R.sub.10               (1b)

Compounds having three six-membered rings:

    R.sub.9 -A.sub.2 -A.sub.3 -A.sub.4 -R.sub.10 (1c)

    R.sub.9 -A.sub.2 -Z.sub.2 -A.sub.3 -A.sub.4 -R.sub.10      (1d)

    R.sub.9 -A.sub.2 -A.sub.3 -Z.sub.3 -A.sub.4 -R.sub.10      (1e)

    R.sub.9 -A.sub.2 -Z.sub.2 -A.sub.3 -Z.sub.3 -A.sub.4 -R.sub.10(1f)

Compounds having four six-membered rings:

    R.sub.9 -A.sub.1 -A.sub.2 -A.sub.3 -A.sub.4 -R.sub.10      (1g)

    R.sub.9 -A.sub.1 -Z.sub.1 -A.sub.2 -A.sub.3 -A.sub.4 -R.sub.10(1h)

    R.sub.9 -A.sub.1 -A.sub.2 -Z.sub.2 -A.sub.3 -A.sub.4 -R.sub.10(1i)

    R.sub.9 -A.sub.1 -A.sub.2 -A.sub.3 -Z.sub.3 -A.sub.4 -R.sub.10(1j)

    R.sub.9 -A.sub.1 -Z.sub.1 -A.sub.2 -Z.sub.2 -A.sub.3 -A.sub.4 -R.sub.10(1k)

    R.sub.9 -A.sub.1 -Z.sub.1 -A.sub.2 -A.sub.3 -Z.sub.3 -A.sub.4 -R.sub.10(1l)

    R.sub.9 -A.sub.1 -A.sub.2 -Z.sub.2 -A.sub.3 -Z.sub.3 -A.sub.4 -R.sub.10(1m)

    R.sub.9 -A.sub.1 -Z.sub.1 -A.sub.2 -Z.sub.2 -A.sub.3 -Z.sub.3 -A.sub.4 -R.sub.10                                                 (1n)

Among these compounds, compounds expressed particularly by the formula(1a), (1c), or (1g) are preferable for achieving the objects of thepresent invention.

Compounds expressed by the formula (la) can further be developed intothe compounds expressed by the following formula (1aa) or (1ab):

    R.sub.9 -Cyc-Cyc-R.sub.10                                  (1aa)

    R.sub.9 -Cyc-Phe-R.sub.10                                  (1ab)

Among these compounds, compounds expressed by the formula (1aa) areespecially preferable. Since these two-ring system compounds areremarkably low in viscosity while having a comparatively high clearingpoint, and exhibit a medium degree of Δε and large K₃₃ /K₁₁, it ispossible to considerably reduce only the viscosity of liquid crystalcompositions without lowering their clearing point when such compoundsare used as a component of the compositions.

Compounds expressed by the formula (1c) can further be developed intothe compounds expressed by the following formulas (1ca) to (1cc):

    R.sub.9 -Cyc-Cyc-Cyc-R.sub.10                              (1ca)

    R.sub.9 -Cyc-Phe-Cyc-R.sub.10                              (1cb)

    R.sub.9 -Cyc-Phe-Phe-R.sub.10                              (1cc)

Among these compounds, the compounds expressed by the formula (1ca) or(1cb) are especially preferable. These three-ring system compounds alsoexhibit properties similar to those of the two-ring system compoundsdescribed above, and clearing point of liquid crystal compositions canfurther be raised by using such compounds as a component of thecompositions.

Also, compounds expressed by the formula (1g) can further be developedinto the compounds expressed by one of the following formulas (1ga) to(1gc):

    R.sub.9 -Cyc-Cyc-Cyc-Cyc-R.sub.10                          (1ga)

    R.sub.9 -Cyc-Phe-Phe-Cyc-R.sub.10                          (1gb)

    R.sub.9 -Cyc-Phe-Phe-Phe-R.sub.10                          (1gc)

Among these compounds, the compounds expressed by the formula (1gb) or(1gc) are especially preferable. Since these four-ring system compoundsare also comparatively low in viscosity while having a high clearingpoint, it is possible to raise only clearing point of liquid crystalcompositions while maintaining their viscosity by using such compoundsas a component of the compositions.

While compounds expressed by the formula (1aa), (1ca), (1cb), (1gb), or(1gc) can be said to be preferable examples as described above,compounds expressed by one of the following formulas (1-1) to (1-4) canbe mentioned as more preferable ones among such compounds as mentionedjust above. ##STR11##

While R₉ in all compounds described above is an alkenyl group having 3to 12 carbon atoms wherein one hydrogen atom at ω-position is replacedby fluorine atom, particularly preferable groups among them are3-fluoro-1-propenyl, 4-fluoro-1-butenyl, 5-fluoro-pentenyl,6-fluoro-3-hexenyl, and 7-fluoro-3-heptenyl. While R₁₀ is an alkenylgroup having 2 to 12 carbon atoms, particularly preferable groups amongthem are ethenyl, 1-propenyl, 3-butenyl, and 3-pentenyl.

While the liquid crystal compositions provided by the present inventionmay comprise only a first component comprising at least onefluoroalkenyl derivative of liquid crystalline compound expressed by thegeneral formula (1), the compositions preferably comprise, as a secondcomponent, at least one compound selected from the group consisting ofthe compounds expressed by any one of the general formulas (2), (3), and(4) (hereinafter referred to as second A component) and/or at least onecompound selected from the group consisting of the compounds expressedby any one of the general formulas (5), (6), (7), (8), and (9)(hereinafter referred to as second B component) in addition to the firstcomponent. Further, one or more known compounds may be mixed to theliquid crystal compositions of the present invention as a thirdcomponent for the purpose of adjusting V_(th), temperature range of aliquid crystal phase, Δn, Δε, and viscosity.

As preferable examples of the compounds included in the general formula(2), (3), or (4) among the second A component, compounds expressed byone of the formulas (2-1) to (2-15), (3-1) to (3-48), and (4-1) to(4-55) can be mentioned, respectively. ##STR12## wherein R₁ has the samemeaning as that described above.

Compounds expressed by one of the general formulas (2) to (4) exhibit apositive Δε, and are very excellent in heat stability and chemicalstability.

Amount of the compounds to be used is suitably 1 to 99% by weight,preferably 10 to 97% by weight, and more desirably 40 to 95% by weightbased on the total amount of liquid crystal composition.

Next, as preferable examples of the compounds included in one of thegeneral formulas (5), (6), and (7) among the second B component, thecompounds expressed by one of the formulas (5-1) to (5-24), (6-1) to(6-3), and (7-1) to (7-28) can be mentioned, respectively. ##STR13##wherein R₂, R₃, and R₄ have the same meaning as described above.

Compounds expressed by one of the general formulas (5) to (7) have alarge positive value of Δε, and are used as a component of thecompositions particularly for the purpose of lowering V_(th). Thecompounds are used also for the purpose of adjusting viscosity, for thepurpose of adjusting Δn and expanding the temperature range of a liquidcrystal phase, and further for the purpose of improving the steepness.

As preferable examples of the compounds included in the general formula(8) or (9) among the second B component, the compounds expressed by oneof the formulas (8-1) to (8-8), and (9-1) to (9-13) can be mentioned,respectively. ##STR14## wherein R₅ and R₆ have the same meaning as thosedescribed above.

Compounds expressed by the general formula (8) or (9) have a negative orslightly positive Δε. Among them, the compounds expressed by the generalformula (8) are used as a component of liquid crystal compositions forthe purpose of principally reducing viscosity and/or adjusting An.Compounds expressed by the general formula (9) are used for the purposeof widening a nematic range such as raising clearing point and/oradjusting Δn.

Compounds expressed by one of the general formulas (5) to (9) areindispensable particularly when liquid crystal compositions for STNdisplay mode or ordinary TN display mode are produced. While thecompounds can be used in any amount in the range of 1 to 99% by weightwhen liquid crystal compositions for ordinary TN display mode or STNdisplay mode are produced, the amount is preferably in the range of 10to 97% by weight and more desirably in the range of 40 to 95% by weight.Also at that time, compounds expressed by one of the general formulas(2) to (4) may be used together as a part of the compositions.

Liquid crystal compositions provided by the present invention preferablycomprise at least one liquid crystalline compounds expressed by thegeneral formula (1) in the ratio of 0.1 to 99.9% by weight to developexcellent properties. The liquid crystal compositions are produced bymethods which are conventional by themselves. For instance, thecompositions are generally produced by methods such as a method in whichvarious components are dissolved with one another at a high temperature,and a method in which components are dissolved and mixed in an organicsolvent for the components and then the solvent is distilled off under areduced pressure.

Also, the compositions of the present invention are improved andoptimized due to their intended uses by adding a suitable additive whennecessary. Such an additive is well known in the art and described inthe literature in detail.

Further, the liquid crystal compositions can be used as ones forguest-host (GH) mode when a dichroic dye such as merocyanine type,styryl type, azo type, azomethine type, azoxy type, quinophthalone type,anthraquinone type, or tetrazine type is added. The liquid crystalcompositions of the present invention can be used for liquid crystalcompositions of an electrically controlled birefringence (ECB) mode ordynamic scattering (DS) mode including for NCAP which is prepared by themicroencapsulation of a nematic liquid crystal and for polymer dispersedliquid crystal display devices (PDLCD) represented by polymer net workliquid crystal display devices (PNLCD) prepared by forming a polymer ofthree-dimensional reticulated structure in a liquid crystal.

As examples of the nematic liquid crystal compositions comprising thecompound of the present invention, the following Composition Examples 1through 15 can be mentioned.

In each of the following composition examples, compounds are indicatedaccording to the instructions shown in Table 1 below. That is, left handside terminal groups are indicated by s-, sO-, sOt-, Vs-, sVt-, V-, sV-,or FsV (both s and t are an integer of 1 or greater); bonding groups by2, E, T, or V; ring structures by B, B(F), B(F,F), H, Py, or D; andright hand side terminal groups are indicated by -F, -CL, -C, -OCF₃,-OCF₂ H, -w, -Ow, -wOx, -EMe, -V, -Vw, -wV, or -wVx (both w and x are aninteger of 1 or greater), respectively. In the followings, the compoundnumber added to some of the compounds are used to indicate the fact thatthe compounds having the same number in the following CompositionExamples and Examples below are the same.

                  TABLE 1                                                         ______________________________________                                        Left side                                                                     terminal group Symbol   Bonding group                                                                            Symbol                                     ______________________________________                                        C.sub.s H.sub.2s+1 --                                                                        s--      --CH.sub.2 CH.sub.2 --                                                                   2                                          C.sub.s H.sub.2s+1 O--                                                                       sO--     --COO--    E                                          C.sub.s H.sub.2s+1 OC.sub.t H.sub.2t --                                                      sOt--    --C.tbd.C--                                                                              T                                          CH.sub.2 ═CHC.sub.s H.sub.2s --                                                          Vs--     --CH═CH--                                                                            V                                          C.sub.s H.sub.2s+1 CH═CHC.sub.t H.sub.2t --                                              sVt--                                                          CH.sub.2 ═CH--                                                                           V--                                                            C.sub.s H.sub.2s+1 CH═CH--                                                               sV--                                                           FC.sub.s H.sub.2s CH═CH--                                                                FsV--                                                          ______________________________________                                                            Right side                                                Ring structure                                                                            Symbol  terminal group  Symbol                                    ______________________________________                                        1 #STR15##  B       --F --Cl        --F --CL                                  2 #STR16##  B(F)    --CN --OCF.sub.3                                                                              --C --OCF3                                3 #STR17##  B(F,F)  --OCF.sub.2 H --C.sub.w H.sub.2w+1 --OC.sub.w                                 H.sub.2w+1      --OCF2H --w --Ow                          4 #STR18##  H       --C.sub.w H.sub.2w OC.sub.x H.sub.2x+1                                                        --wOx                                     5 #STR19##  Py      --COOCH.sub.3 --CH═CH.sub.2                                                               --EMe --V                                 6 #STR20##  D       --CH═CHC.sub.w H.sub.2w+1 --C.sub.w H.sub.2w                              CH═CH.sub.2 --C.sub.w H.sub.2w CH═CHC.sub.x                           H.sub.2x+1      --Vw --wV --wVx                           ______________________________________                                    

    ______________________________________                                        Composition Example 1                                                         F3V-HH-2V         (No. 11) 5.0%                                               3O1-BEB(F)-C               11.0%                                              V2-HB-C                    11.0%                                              3-HB-O2                    3.0%                                               2-BTB-O1                   6.8%                                               3-BTB-O1                   6.8%                                               4-BTB-O1                   6.8%                                               4-BTB-O2                   6.8%                                               5-BTB-O1                   6.8%                                               3-H2BTB-3                  3.0%                                               3-H2BTB-4                  3.0%                                               3-HB(F)TB-2                6.0%                                               3-HB(F)TB-3                6.0%                                               3-HB(F)TB-4                6.0%                                               2-PyBH-3                   4.0%                                               3-PyBH-3                   4.0%                                               3-PyBB-2                   4.0%                                               Composition Example 2                                                         F3V-HH-2V         (No. 11) 5.0%                                               F3V-HH-V1         (No. 10) 4.0%                                               F3V-HHH-V         (No. 69) 3.0%                                               F3V-HBBH-V1       (No. 190)                                                                              3.0%                                               V2-HB-C                    9.0%                                               1V2-HB-C                   9.0%                                               3-HB-C                     14.0%                                              1O1-HB-C                   8.0%                                               2O1-HB-C                   4.0%                                               2-HHB-C                    5.0%                                               3-HHB-C                    5.0%                                               3-HH-4                     5.0%                                               3-HH-EMe                   3.0%                                               1O1-HH-5                   4.0%                                               2-BTB-O1                   11.0%                                              3-HHB-1                    4.0%                                               3-HHB-3                    4.0%                                               Composition Example 3                                                         F3V-HH-2V         (No. 11) 7.0%                                               F3V-HB-2V         (No. 31) 8.0%                                               2O1-BEB(F)-C               4.0%                                               3O1-BEB(F)-C               12.0%                                              5O1-BEB(F)-C               4.0%                                               1V2-BEB (F,F)-C            15.0%                                              3-HHEB-F                   5.0%                                               5-HHEB-F                   5.0%                                               3-HBEB-F                   6.0%                                               3-HHB-F                    3.0%                                               3-HHB-1                    8.0%                                               3-HHB-3                    6.0%                                               3-HHB-O1                   4.0%                                               3-H2BTB-2                  4.0%                                               3-H2BTB-3                  4.0%                                               3-HB(F)VB-2                5.0%                                               Composition Example 4                                                         F3V-HH-V1         (No. 10) 5.0%                                               F3V-HH-2V         (No. 11) 5.0%                                               F3V-HH-2V1        (No. 12) 4.0%                                               F3V-HHH-V1        (No. 70) 2.0%                                               F3V-HBH-2V1       (No. 92) 4.0%                                               2-HB(F)-C                  15.0%                                              2-HEB-F                    2.5%                                               3-HEB-F                    2.5%                                               3-HHEB-F                   5.0%                                               5-HHEB-F                   5.0%                                               2-HHB(F)-C                 10.0%                                              3-HHB(F)-C                 10.0%                                              2-HHB(F)-F                 10.0%                                              3-HHB(F)-F                 10.0%                                              5-HHB(F)-F                 10.0%                                              Composition Example 5                                                         F3V-HH-2V         (No. 11) 6.0%                                               F3V-HB-V          (No. 29) 4.0%                                               F3V-HB-V1         (No. 30) 4.0%                                               F3V-HBBH-2V       (No. 191)                                                                              3.0%                                               F3V-HBBB-V        (No. 209)                                                                              3.0%                                               3-HB(F)-C                  4.0%                                               3-HB-C                     21.0%                                              3-HHB-C                    5.0%                                               5-PyB-F                    10.0%                                              2-BTB-1                    6.0%                                               3-HH-4                     5.0%                                               3-HH-5                     5.0%                                               3-HHB-1                    10.0%                                              3-HHB-3                    10.0%                                              3-HEBEB-2                  2.0%                                               3-HEBEB-F                  2.0%                                               Composition Example 6                                                         F3V-HB-V          (No. 29) 5.0%                                               F3V-HBH-2V        (No. 91) 5.0%                                               2-BB-C                     8.0%                                               4-BB-C                     6.0%                                               2-HB-C                     10.0%                                              3-HB-C                     13.0%                                              3-HHB-F                    5.0%                                               2-HHB-C                    5.0%                                               3-HHB-C                    6.0%                                               5-PyB-F                    6.0%                                               3-PyBB-F                   6.0%                                               2-HHB-1                    5.0%                                               3-HHB-1                    5.0%                                               3-HHB-3                    10.0%                                              3-HHB-O1                   5.0%                                               Composition Example 7                                                         F3V-HH-2V         (No. 11) 5.0%                                               F3V-HB-2V1        (No. 32) 5.0%                                               3-DB-C                     10.0%                                              4-DB-C                     12.0%                                              5-DB-C                     8.0%                                               2-BEB-C                    10.0%                                              5-PyB(F)-F                 10.0%                                              3-PyB-2                    2.0%                                               3-PyB-O2                   2.0%                                               3-HEB-O4                   5.0%                                               4-HEB-O2                   3.0%                                               3-HEB-O2                   2.0%                                               1O-BEB-2                   2.0%                                               5-HEB-1                    3.0%                                               4-HEB-4                    3.0%                                               3-HHB-3                    8.0%                                               2-PyBH-3                   6.0%                                               3-HBEBB-C                  2.0%                                               3-HHEBB-C                  2.0%                                               Composition Example 8                                                         F3V-HH-2N         (No. 11) 10.0%                                              7-HB(F,F)-F                5.0%                                               3-H2HB(F,F)-F              10.0%                                              4-H2HB(F,F)-F              8.0%                                               5-H2HB(F,F)-F              10.0%                                              3-HHB(F,F)-F               8.0%                                               3-HH2B(F,F)-F              12.0%                                              5-HH2B(F,F)-F              10.0%                                              3-HBB(F,F)-F               12.0%                                              5-HBB(F,F)-F               10.0%                                              3-HHBB(F,F)-F              2.0%                                               3-HH2BB(F,F)-F             3.0%                                               Composition Example 9                                                         F3V-HH-2V         (No. 11) 5.0%                                               F3V-HB-V          (No. 29) 5.0%                                               F3V-HHH-V1        (No. 70) 2.0%                                               7-HB(F)-F                  12.0%                                              2-HHB(F)-F                 12.0%                                              3-HHB(F)-F                 12.0%                                              5-HHB(F)-F                 12.0%                                              2-H2HB(F)-F                5.6%                                               3-H2HB(F)-F                2.8%                                               5-H2HB(F)-F                5.6%                                               2-HBB(F)-F                 6.5%                                               3-HBB(F)-F                 6.5%                                               5-HBB(F)-F                 13.0%                                              Composition Example 10                                                        F3V-HH-V          (No. 9)  4.0%                                               F3V-HH-V1         (No. 10) 4.0%                                               F3V-HBBH-V        (No. 189)                                                                              4.0%                                               5-H2B(F)-F                 5.0%                                               2-HHB(F)-F                 10.0%                                              3-HHB(F)-F                 10.0%                                              5-HHB(F)-F                 10.0%                                              2-H2HB(F)-F                4.0%                                               3-H2HB(F)-F                2.0%                                               5-H2HB(F)-F                4.0%                                               3-H2HB(F,F)-F              6.0%                                               4-H2HB(F,F)-F              5.0%                                               5-H2HB(F,F)-F              5.0%                                               3-H2BB(F,F)-F              5.0%                                               5-H2BB(F,F)-F              5.0%                                               3-HHB(F,F)-F               8.0%                                               3-HHEB(F,F)-F              6.0%                                               5-HBEB(F,F)-F              3.0%                                               Composition Example 11                                                        F3V-HH-2V         (No. 11) 4.0%                                               F3V-HB-2V         (No. 31) 5.0%                                               F3V-HBH-V         (No. 89) 3.0%                                               F3V-HBBB-2V       (No. 211)                                                                              3.0%                                               7-HB-CL                    7.0%                                               2-HBB(F)-F                 5.0%                                               3-HBB(F)-F                 5.0%                                               5-HBB(F)-F                 10.0%                                              4-H2BB(F)-F                6.0%                                               5-H2BB(F)-F                6.0%                                               2-HHB-CL                   5.0%                                               4-HHB-CL                   10.0%                                              3-HBB(F,F)-F               11.0%                                              5-HBB(F,F)-F               10.0%                                              3-HB(F)VB-2                5.0%                                               3-HB(F)VB-3                5.0%                                               Composition Example 12                                                        F3V-HB-V1         (No. 30) 6.0%                                               F3V-HB-2V1        (No. 32) 4.0%                                               2-HHB(F)-F                 6.6%                                               3-HHB(F)-F                 6.7%                                               5-HHB(F)-F                 6.7%                                               3-HHB(F,F)-F               7.0%                                               5-HHB(F,F)-F               7.0%                                               3-H2HB(F,F)-F              7.0%                                               4-H2HB(F,F)-F              7.0%                                               5-H2HB(F,F)-F              7.0%                                               3-HH2B(F,F)-F              12.0%                                              5-HH2B(F,F)-F              8.0%                                               2-HBB-F                    4.0%                                               3-HBB-F                    5.0%                                               3-HHEBB-F                  3.0%                                               1O1-HBBH-3                 3.0%                                               Composition Example 13                                                        F3V-HH-2V         (No. 11) 5.0%                                               F3V-HB-V1         (No. 30) 4.0%                                               F3V-HBBH-V        (No. 189)                                                                              4.0%                                               5-HB-F                     7.0%                                               5-HH-O1                    5.0%                                               3-HHB-OCF2H                3.0%                                               5-HHB-OCF2H                4.0%                                               3-HHB(F,F)-OCF2H           10.0%                                              5-HHB(F,F)-OCF2H           11.0%                                              2-HHB-OCF3                 4.0%                                               3-HHB-OCF3                 7.0%                                               4-HHB-OCF3                 6.0%                                               5-HHB-OCF3                 6.0%                                               3-HH2B(F)-F                7.0%                                               5-HH2B(F)-F                9.0%                                               3-HHEB(F)-F                6.0%                                               5-HB(F)BH-3                2.0%                                               Composition Example 14                                                        F3V-HH-V          (No. 9)  5.0%                                               F3V-HH-V1         (No. 10) 6.0%                                               F3V-HB-V          (No. 29) 6.0%                                               F3V-HBBB-V1       (No. 210)                                                                              3.0%                                               V-HB-C                     10.0%                                              1V-HB-C                    5.0%                                               3-BB-C                     5.0%                                               5-BB-C                     5.0%                                               2-HB(F)-C                  5.0%                                               4-BB-3                     3.0%                                               5-H2B-02                   5.0%                                               3-BEB-C                    5.0%                                               5-HEB-03                   8.0%                                               5-BBB-C                    5.0%                                               4-BPyB-C                   4.0%                                               4-BPyB-5                   4.0%                                               5-HB2B-4                   4.0%                                               5-HBB2B-3                  4.0%                                               1V-HH-1O1                  4.0%                                               1V2-HBB-3                  4.0%                                               Composition Example 15                                                        F3V-HH-2V         (No. 11) 5.0%                                               F3V-HHH-2V        (No. 71) 2.0%                                               F3V-HBBH-V        (No. 189)                                                                              3.0%                                               4-HEB(F)-F                 10.0%                                              5-HEB(F)-F                 8.0%                                               2-BEB(F)-C                 5.0%                                               3-BEB(F)-C                 5.0%                                               4-BEB(F)-C                 8.0%                                               5-BEB(F)-C                 8.0%                                               1O3-HB(F)-C                6.0%                                               3-HHEB(F)-F                5.0%                                               5-HHEB(F)-F                5.0%                                               2-HBEB(F)-C                5.0%                                               3-HBEB(F)-C                5.0%                                               4-HBEB(F)-C                5.0%                                               5-HBEB(F)-C                5.0%                                               3-HBTB-2                   4.0%                                               V2-HH-3                    3.0%                                               V2-HHB-1                   3.0%                                               Composition Example 16                                                        F3V-HH-V1F        (No. 242)                                                                              5.0%                                               F2V-HB-2VF        (No. 251)                                                                              5.0%                                               3-DB-C                     10.0%                                              4-DB-C                     12.0%                                              5-DB-C                     8.0%                                               2-BEB-C                    10.0%                                              5-PyB(F)-F                 10.0%                                              3-PyB-2                    2.0%                                               3-PyB-O2                   2.0%                                               3-HEB-O4                   5.0%                                               4-HEB-O2                   3.0%                                               3-HEB-O2                   2.0%                                               1O-BEB-2                   2.0%                                               5-HEB-1                    3.0%                                               4-HEB-4                    3.0%                                               3-HHB-3                    8.0%                                               2-PyBH-3                   6.0%                                               3-HBEBB-C                  2.0%                                               3-HHEBB-C                  2.0%                                               ______________________________________                                    

Compounds of the present invention expressed by the general formula (1)can readily be produced by suitably selecting chemical procedures ofordinary organic synthesis, for example, those described in OrganicSynthesis, Organic Reactions, or Jikken Kagaku Kouza (Course of ChemicalExperiment), and using them in combination.

That is, methoxyethyltriphenylphosphonium halide (2) is first reactedwith compound (1) in an ether type solvent such as THF and diethyl etherin the presence of a base such as sodium methylate, potassium-t-butoxide(t-BuOK), and butyl lithium to obtain compound (3) by using the Wittigreaction described, for instance, in Organic Reactions, Vol. 14, Chapter3. Subsequently, the compound (3) is reacted with a mineral acid such ashydrochloric acid and sulfuric acid, or an organic acid such as formicacid, acetic acid, or p-toluenesulfonic acid to obtain aldehydederivative (4), and then the aldehyde derivative (4) andalkyltriphenylphosphonium halide (5) are subjected to the Wittigreaction under the same conditions as those described above, to obtainintermediate compound (6). ##STR21##

Also, compound (8) (wherein n is an integer of 1 to 5) can be obtainedfrom the reaction between compound (1) and derivative oftriphenylphosphonium halide (7) in the same manner as in the case wherethe compound (3) described above is obtained. Subsequently, the olefinportion of the compound (8) is reduced by a hydrogen-reduction in thepresence of a reducing catalyst to obtain compound (9) and then amineral acid such as hydrochloric acid and sulfuric acid, or an organicacid such as formic acid, acetic acid, and p-toluenesulfonic acid isreacted to the compound (9) to remove the protecting group therebyobtain aldehyde derivative (10). Thereafter, the aldehyde derivative(10) and alkyltriphenylphosphonium halide (5) are subjected to theWittig reaction in the same manner as in the case where the compound (6)described above is obtained to produce intermediate compound (11).##STR22##

Compounds of the present invention can be produced by using theintermediate compound (6) or (11) described above.

That is, diisobutylaluminum hydride (hereinafter abbreviated as DIBAL)is first reacted to intermediate compound (6) to obtain aldehydederivative (12), and then the same reaction as in the case where thecompound (3) is obtained is repeatedly applied m times to the aldehydederivative (12) to produce aldehyde derivative (13) in which number ofmethylene chain is increased by m. Then, the aldehyde derivative (13)and fluoroalkyltriphenylphosphonium halide (14) are subjected to theWittig reaction to obtain compound (15), and then a mineral acid such ashydrochloric acid and sulfuric acid, and benzenesulfinic acid salt orp-toluenesulfinic acid salt is reacted to the compound to isomerize thecompound thereby produce an example of the compounds of the presentinvention (1-1). ##STR23##

Also, another example of the compounds of the present invention (1-2)can be produced by conducting the same series of the procedures as inthe case where the compound (1-1) is obtained with the exception thatintermediate compound (11) is used in place of intermediate compound(6). ##STR24##

Now, the present invention will be described in more detail withreference to Examples. However, it should be understood that the presentinvention is by no means restricted to such specific Examples.

In each of the Examples, structure of compounds was confirmed by nuclearmagnetic resonance spectrum (hereinafter abbreviated as ¹ H-NMR) and/ormass spectrum (hereinafter abbreviated as MS). In MS, M+ indicatesmolecular ion peak and the numeral in parenthesis indicates ionstrength, respectively. Further, Cr indicates a crystal phase, S asmectic phase, N a nematic phase, and. Iso indicates an isotropic liquidphase, and all unit of phase transition temperature is ° C.

EXAMPLE 1

Preparation of 1-(3-butenyl)-trans-4-(trans-4-((E) -(5-fluoro-1-pentenyl)cyclohexyl)cyclohexane (Compound expressed by thegeneral formula (1) wherein both rings A₃ and A₄ representtrans-1,4-cyclohexylene group, Z₃ represents a single bond, l is 3, bothm and o are 0, n is 2, and both p and q are 0 (Compound No. 11))

First stage

After a mixture of 247.8 g (545.4 mmol) of2-(1,3-dioxane-2-yl)ethyltriphenylphosphonium bromide and 2500 ml of THFwas cooled down to -50° C. under nitrogen gas stream, 67.3 g (599.8mmol) of t-BuOK was added thereto and stirred for 1 hour. To the mixturewas added dropwise a solution of 100.0 g (419.6 mmol) oftrans-4-(4-cyclohexanone-1-yl)cyclohexane carboxylic acid methyl esterin 1000 ml of THF while maintaining a temperature below -50° C. Afterthe finish of the dropping, the reaction temperature was graduallyraised up to room temperature and the mixture was further stirred for 5hours. After the solvent was distilled off under a reduced pressure and500 ml of water was added, it was extracted with 500 ml of toluene.After the organic layer thus obtained was washed with 200 ml of waterthrice, the layer was dried over anhydrous magnesium sulfate. Thesolvent was distilled off under a reduced pressure and the residue wassubjected to silica gel column chromatography (eluent: mixed solvent ofethyl acetate/heptane=1/9) to obtain 119.4 g of a crude derivative ofcyclohexylidene (16). ##STR25## Second stage

After 119.4 g (357.0 mmol) of this crude product was dissolved in 1,200ml of a mixed solvent of toluene/ethanol (4/1), a catalyst was addedthereto and stirred at room temperature under a condition of hydrogengas pressure of 1 to 2 kg/cm². When the amount of consumed hydrogenreached 8,000 ml, the stirring was terminated and the catalyst wasfiltered off. The solvent was distilled off under a reduced pressure,the residue was subjected to silica gel column chromatography (eluent:toluene and ethyl acetate), and the crude product thus obtained wasrecrystallized from a mixed solvent of ethyl acetate/Solmix/heptane(1/2/10) to obtain 74.9 g of trans-4-(trans-4-(2-(1,3-dioxane-2-yl)ethyl)cycloyhexyl)cyclohexane carboxylic acid methylester.

Third stage

This product in an amount of 74.9 g (221.2 mmol) was dissolved in 750 mlof toluene, 101.7 g (2.21 mmol) of formic acid was added thereto, heatedto reflux for 5 hours, 600 ml of water was added, and then the liquidmixture thus obtained was separated into layers with a separatingfunnel. The organic layer thus obtained was washed with 600 ml of waterthrice, dried over anhydrous magnesium sulfate, and then the solvent wasdistilled off under a reduced pressure to obtain 58.9 g of a crudetrans.4-(trans-4-(2-formylethyl)cyclohexyl)cyclohexane carboxylic acidmethyl ester.

Fourth stage

A solution of 58.9 g (210.0 mmol) of this product in 500 ml of THF wasadded dropwise, while maintaining a temperature below -50° C., to thefollowing mixture, that is, the mixture obtained by cooling a liquidmixture of 97.5 g (272.9 mmol) of methyltriphenylphosphonium bromidewith 1,000 ml of THF down to -50° C. under nitrogen gas stream, adding33.7 g (300.3 mmol) of t-BuOK thereto, and stirring them for 1 hour.After the finish of the dropping, the reaction temperature was graduallyraised up to room temperature, and further shirred for 5 hours. Thesolvent was distilled off under a reduced pressure, 250 ml of water wasadded to the residue, and then extracted with 250 ml of toluene. Afterthe organic layer thus obtained was washed with 100 ml of water thriceand dried over anhydrous magnesium sulfate, the solvent was distilledoff under a reduced pressure, and then the residue was subjected tosilica gel column chromatography (eluent: mixed solvent of ethylacetate/heptane=1/1) to obtain 50.3 g of a crudetrans-4-(trans-4-(3-butenyl)cyclohexyl)cyclohexane carboxylic acidmethyl ester.

Fifth stage

This crude product in an amount of 50.3 g (180.7 mmol) was dissolved in1,000 ml of toluene, and 181 ml of 1.0 M toluene solution of DIBAL wasadded dropwise thereto at a temperature below -50° C. under nitrogen gasstream. After stirred at the same temperature for 1 hour, the reactionsolution was gradually poured into water to terminate the reaction.Subsequently, it was washed with 700 ml of water thrice and dried overanhydrous magnesium sulfate. The solvent was distilled off under areduced pressure to obtain 27.0 g of a crudetrans-4-(trans-4-(3-butenyl) cyclohexyl)cyclohexylcarbaldehyde.

Sixth stage

Solution of 27.0 g (108.7 mmol) of this product in 300 ml of THF wasadded dropwise, while maintaining a temperature below -50° C., to thefollowing mixture, that is, the mixture obtained by cooling a liquidmixture of 58.3 g (139.7 mmol) of 4-fluorobutyltriphenylphosphoniumbromide with 600 ml of THF down to -50° C. under nitrogen gas stream,adding 17.3 g (154.2 mol) of t-BuOK, and stirring for 1 hour. After thefinish of the dropping, the reaction temperature was gradually raised upto room temperature and further stirred for 5 hours. The solvent wasdistilled off under a reduced pressure, 150 ml of water was addedthereto, and extracted with 150 ml of toluene. The organic layer thusobtained was washed with 50 ml of water thrice and dried over anhydrousmagnesium sulfate. The solvent was distilled off under a reducedpressure and the residue was subjected to silica gel columnchromatography (eluent: heptane) to obtain 23.7 g of a crude1-(3-butenyl)-trans-4-(trans-4-((5-fluoro-1-pentenyl)cyclohexyl)cyclohexane.

Seventh stage

This crude product in an amount of 23.7 g (77.3 mmol) was dissolved in250 ml of ethanol, 20.9 g (116.0 mmol) of sodium benzenesulfinate and 19ml of 6N-hydrochloric acid were added thereto and heated to reflux for 4hours. The solvent was distilled off under a reduced pressure, 100 ml ofwater was added to the residue, and then the residue was extracted with150 ml of ethyl acetate. The organic layer was washed with 70 ml ofwater thrice, dried over anhydrous magnesium sulfate, the solvent wasdistilled off under a reduced pressure, and the residue was subjected tosilica gel column chromatography (eluent: heptane) to obtain a crudeproduct of1-(3-butenyl)-trans-4-(trans-4-((E)-(5-fluoro-1-pentenyl)cyclohexyl)cyclohexane. This crude product was recrystallized from Solmix to obtain16.1 g (yield 12.5 %) of the subject compound.

Phase transition temperature: Cr below room temperature S_(B) 81.8 Iso

MS: m/e=306 (M⁺, 15%), 135 (62), 95 (73), 81 (100), 67 (81).

¹ H-NMR: As shown in FIG. 1.

EXAMPLE 2

Preparation of1-ethenyl-trans-4-(trans-4-(trans-4-((E)-(5-fluoro-1-pentenyl)cyclohexyl)cyclohexyl)cyclohexane(Compound expressed by the general formula (1) wherein rings A₂, A₃, andA₄ represent trans-1,4-cyclohexylene group, both Z₂ and Z₃ representsingle bond, Q is 3, m, n, and o are 0, p is 0, and q is 1 (Compound No.69))

First stage

Mixture of 139.1 g (405.8 mmol) of methoxymethyltriphenylphosphoniumchloride with 1,500 ml of THF was cooled down to -50° C. under nitrogengas stream, 50.1 g (446.5 mmol) of t-BuOK was added thereto, and stirredfor 1 hour. To this mixture was added dropwise a solution of 100.0 g(312.0 mmol) oftrans-4-(trans-4-(4-cyclohexanone-1-yl)cyclohexyl)cyclohexane carboxylicacid methyl ester in 1,000 ml of THF while maintaining a temperaturebelow -50° C. After finishing of the dropping, the reaction temperaturewas gradually raised up to room temperature and it was further stirredfor 5 hours. The solvent was distilled off under a reduced pressure, 500ml of water was added thereto, and extracted with 500 ml of toluene. Theorganic layer thus obtained was washed with 200 ml of water thrice anddried over anhydrous magnesium sulfate. The solvent was distilled offunder a reduced pressure and the residue was subjected to silica gelcolumn chromatography (eluent: mixed solvent of ethylacetate/heptane=2/9) to obtain 95.7 g of a crude cyclohexylidenederivative (17). ##STR26## Second stage

After 95.7 g (274.6 mmol) of this crude product was dissolved in 1,000ml of toluene, 126.6 g (2.76 mmol) of formic acid was added thereto andheated to reflux for 5 hours.

To this solution was added 500 ml of water, and the mixture wasseparated into layers with a separating funnel. The organic layer thusobtained was washed with 500 ml of water thrice, dried over anhydrousmagnesium sulfate, and then the solvent was distilled under a reducedpressure to obtain 89.1 g of a crudetrans-4-(trans-4-(trans-4-formylcyclohexyl)cyclohexyl) cyclohexanecarboxylic acid methyl ester.

Third stage

Solution of 89.1 g (266.4 mmol) of this product in 900 ml of THF wasadded dropwise, while maintaining a temperature below -50° C., to thefollowing mixture, that is, the mixture obtained by cooling a liquidmixture of 123.7 g (346.2 mmol) of methyltriphenylphosphonium bromidewith 1,200 ml of THF down to -50° C. under nitrogen gas stream, adding42.7 g (380.5 mmol) of t-BuOK, and stirring for 1 hour. After the finishof the dropping, the reaction temperature was gradually raised up toroom temperature and further stirred for 5 hours. The solvent wasdistilled off under a reduced pressure, 300 ml of water was added to theresidue, and extracted with 250 ml of toluene. The organic layer thusobtained was washed with 300 ml of water thrice and dried over anhydrousmagnesium sulfate. The solvent was distilled off under a reducedpressure and the residue was subjected to silica gel columnchromatography (eluent: mixed solvent of ethyl acetate/heptane=1/5) toobtain 70.9 g of a crudetrans-4-(trans-4-(trans-4-ethenyl)cyclohexyl)cyclohexyl) cyclohexanecarboxylic acid methyl ester.

Fourth stage

This crude product in an amount of 70.9 g (213.2 mmol) was dissolved in1,500 ml of toluene, and 213 ml of 1.0 M toluene solution of DIBAL wasadded dropwise thereto while maintaining a temperature below -50° C.under nitrogen gas stream. After stirred at the same temperature for 1hour, the reaction solution was gradually poured into water to terminatethe reaction, washed with 1,000 ml of water thrice, and then dried overanhydrous magnesium sulfate. The solvent was distilled off under areduced pressure to obtain 36.8 g of a crudetrans-4-(trans-4-(trans-4-ethenylcyclohexyl)cyclohexyl)cyclohexylcarbaldehyde.

Fifth stage

Solution of 36.8 g (121.7 mmol) of this product in 350 ml of THF wasadded dropwise, while maintaining a temperature below -50° C., to thefollowing mixture, that is, the mixture obtained by cooling a liquidmixture of 66.0 g (158.2 mmol) of 4-fluorobutyltriphenylphosphoniumbromide with 700 ml of THF down to -50° C. under nitrogen gas stream,adding 19.5 g (173.8 mmol) of t-BuOK, and stirring for 1 hour. After thefinish of the dropping, the reaction temperature was gradually raised upto room temperature, and further stirred for 5 hours. The solvent wasdistilled off under a reduced pressure, 200 ml of water was addedthereto, and then extracted with 200 ml of toluene. The organic layerthus obtained was washed with 100 ml of water thrice, and dried overanhydrous magnesium sulfate. The solvent was distilled off under areduced pressure, and the residue was subjected to silica gel columnchromatography (eluent: heptane) to obtain 30.7 g of a crude1-ethenyl-trans-4-(trans-4-(trans-4-((5-fluoro-1-pentenyl)cyclohexyl)cyclohexyl)cyclohexane.

Six stage

This crude product in an amount of 30.7 g (85.1 mmol) was dissolved in300 ml of ethanol, 23.0 g (127.7 mmol) of sodium benzenesulfinate and 21ml of 6N-hydrochloric acid were added thereto and then heated to refluxfor 4 hours. The solvent was distilled off under a reduced pressure, 150ml of water was added thereto, and then extracted with 200 ml of ethylacetate. The organic layer thus obtained was washed with 100 ml of waterthrice and then dried over anhydrous magnesium sulfate. The solvent wasdistilled off under a reduced pressure and the residue was subjected tosilica gel column chromatography (eluent: heptane) to obtain a crudeproduct of1-ethenyl-trans-4-(trans-4-(trans-4-((E)-(5-fluoro-1-pentenyl)cyclohexyl)cyclohexyl)cyclohexane.This crude product was recrystallized from Solmix to obtain 19.9 g(yield 17.7%) of the subject compound.

MS: m/e=360 (M⁺)

EXAMPLE 3

Preparation of1-((E)-1-propenyl)-4-(4-(4-(trans-4-((E)-(5-fluoro-1-pentenyl)cyclohexyl)phenyl)phenyl)cyclohexane(Compound expressed by the general formula (1) wherein both rings A₁ andA₄ represent trans-1,4-cyclohexylene group, both rings A₂ and A₃represent phenylene group, Z₁, Z₂ and Z₃ represent single bond, l is 3,both m and n are 0, o is 1, and both p and q are 1 (Compound No. 190))

First stage

Mixture of 114.1 g (332.8 mmol) of methoxymethyltriphenylphosphoniumchloride with 1,000 ml of THF was cooled down to -50° C. under nitrogengas stream, 41.1 g (366.3 mmol) of t-BuOK was added thereto, and thenstirred for 1 hour.

To this mixture was added dropwise a solution of 100.0 g (256.1 mmol) oftrans-4-(4-(4-(4-cyclohexanone-1-yl)phenyl)phenyl)cyclohexane carboxylicacid methyl ester in 1,000 ml of THF while maintaining a temperaturebelow -50° C. After the finish of the dropping, the reaction temperaturewas gradually raised up to room temperature and further stirred for 5hours. The solvent was distilled off under a reduced pressure, 500 ml ofwater was added thereto, and then extracted with 500 ml of toluene.

The organic layer thus obtained was washed with 200 ml of water thriceand then dried over anhydrous magnesium sulfate. The solvent wasdistilled off under a reduced pressure and the residue was subjected tosilica gel column chromatography (eluent: toluene) to obtain 92.2 g of acrude cyclohexylidene derivative (18). ##STR27## Second stage

After 92.2 g (220.3 mmol) of the crude product was dissolved in 1,000 mlof toluene, 101.3 g (2.20 mmol) of formic acid was added thereto andheated to reflux for 5 hours.

To this mixture was added 500 ml of water, the mixture was separatedinto layers with a separating funnel, and it was washed with 500 ml ofwater thrice and then dried over anhydrous magnesium sulfate. Thesolvent was distilled off under a reduced pressure to obtain 82.9 g of acrude trans-4-(4-(4-(trans-4-formylcyclohexyl)phenyl)phenyl)cyclohexanecarboxylic acid methyl ester.

Third stage

Solution of 82.9 g (204.9 mmol) of this product in 800 ml of THF wasadded dropwise, while maintaining a temperature below -50° C., to thefollowing mixture, that is, the mixture obtained by cooling a liquidmixture of 98.9 g (266.3 mmol) of ethyltriphenylphosphonium bromide with1,000 ml of THF down to -50° C. under nitrogen gas stream, adding 29.9 g(266.5 mmol) of t-BuOK, and stirring for 1 hour. After the finish of thedropping, the reaction temperature was gradually raised up to roomtemperature and further stirred for 5 hours. The solvent was distilledoff under a reduced pressure, 300 ml of water was added thereto, andthen extracted with 250 ml of toluene. The organic layer thus obtainedwas washed with 300 ml of water thrice and then dried over anhydrousmagnesium sulfate. The solvent was distilled off under a reducedpressure and the residue was subjected to silica gel columnchromatography (eluent: toluene) to obtain 70.8 g of a crudetrans-4-(4-(4-(trans-4-(1-propenyl)cyclohexyl)phenyl)phenyl)cyclohexanecarboxylic acid methyl ester.

Fourth stage

This crude product in an amount of 70.8 g (169.9 mmol) was dissolved in1,500 ml of toluene, and 170 ml of 1.0 M toluene solution of DIBAL wasadded dropwise thereto while maintaining a temperature below -50° C.under nitrogen gas stream. After stirred at the same temperature for 1hour, the reaction solution was gradually poured into water to terminatethe reaction, washed with 1,000 ml of water thrice, and then dried overanhydrous magnesium sulfate. The solvent was distilled off under areduced pressure to obtain 40.1 g of a crudetrans-4-(4-(4-(trans-4-(1-propenyl)cyclohexyl)phenyl)phenyl)cyclohexylcarbaldehyde.

Fifth stage Solution of 40.1 g (103.7 ml) of this product in 400 ml ofTHF was added dropwise, while maintaining a temperature below -50° C.,to the following mixture, that is, the mixture obtained by cooling aliquid mixture of 56.3 g (134.9 mmol) of4-fluorobutyltriphenylphosphonium bromide with 600 ml of THF down to-50° C., adding 16.6 g (147.9 mmol) of t-BuOK, and stirring for 1 hour.After the finish of the dropping, the reaction temperature was graduallyraised up to room temperature and further stirred for 5 hours. Thesolvent was distilled off under a reduced pressure, 200 ml of water wasadded, and then extracted with 200 ml of toluene. The organic layer thusobtained was washed with 100 ml of water thrice and then dried overanhydrous magnesium sulfate. The solvent was distilled off under areduced pressure and the residue was subjected to silica gel columnchromatography (eluent: toluene) to obtain 31.4 g of a crude1-(1-propenyl)-trans-4-(4-(4-(trans-4-((5-fluoro-1-pentenyl)cyclohexyl)phenyl)phenyl)cyclohexane.

Six stage

This crude product in an amount of 31.4 g (70.6 mmol) was dissolved in300 ml of ethanol, 38.2 g (212.0 mmol) of sodium benzenesulfinate and 36ml of 6N-hydrochloric acid were added thereto, and heated to reflux for4 hours. The solvent was distilled off under a reduced pressure, 150 mlof water was added, and then extracted with 200 ml of ethyl acetate. Theorganic layer thus obtained was washed with 100 ml of water thrice andthen dried over anhydrous magnesium sulfate. The solvent was distilledoff under a reduced pressure and the residue was subjected to silica gelcolumn chromatography (eluent: toluene) to obtain a crude product of1-((E)-1-propenyl)-trans-4-(4-(4-(trans-4-((E)-(5-fluoro-1-pentenyl)cyclohexyl)phenyl)phenyl)cyclohexane.This crude product was recrystallized from Solmix to obtain 18.8 g(yield 16.5%) of the subject compound.

MS: m/e=444 (M⁺)

According to the methods of Examples 1 to 3, the following compounds(Compound No. 1 to Compound No. 240) can be prepared. In the followingTables, each compound was designated by assuming that compoundsexpressed by the general formula (1) were decomposed into unit portionsin turn and then making unit chemical formulas of specific compoundscorrespond to the unit portions. In the Tables, compounds (Compound Nos.11, 69, and 190) obtained in Examples 1 to 3 are also shown together.

                                      TABLE 2                                     __________________________________________________________________________    7 #STR28##       (A.sub.1 --Z.sub.1).sub.p                                                          (A.sub.2 --Z.sub.2).sub.q                                                          A.sub.3 --Z.sub.3 --A.sub.4                                                               8 #STR29##                             __________________________________________________________________________     1                                                                              9 #STR30##                                                                                             0 #STR31##                                                                                1 #STR32##                              2                                                                              9 #STR33##                                                                                             0 #STR34##                                                                                2 #STR35##                              3                                                                              9 #STR36##                                                                                             0 #STR37##                                                                                3 #STR38##                              4                                                                              9 #STR39##                                                                                             0 #STR40##                                                                                4 #STR41##                              5                                                                              5 #STR42##                                                                                             0 #STR43##                                                                                1 #STR44##                              6                                                                              5 #STR45##                                                                                             0 #STR46##                                                                                2 #STR47##                              7                                                                              5 #STR48##                                                                                             0 #STR49##                                                                                3 #STR50##                              8                                                                              5 #STR51##                                                                                             0 #STR52##                                                                                4 #STR53##                              9                                                                              6 #STR54##                                                                                             0 #STR55##                                                                                1 #STR56##                             10                                                                              6 #STR57##                                                                                             0 #STR58##                                                                                2 #STR59##                             11                                                                              6 #STR60##                                                                                             0 #STR61##                                                                                7 #STR62##                             12                                                                              6 #STR63##                                                                                             0 #STR64##                                                                                4 #STR65##                             13                                                                              8 #STR66##                                                                                             0 #STR67##                                                                                1 #STR68##                             14                                                                              8 #STR69##                                                                                             0 #STR70##                                                                                2 #STR71##                             15                                                                              8 #STR72##                                                                                             0 #STR73##                                                                                3 #STR74##                             16                                                                              8 #STR75##                                                                                             0 #STR76##                                                                                4 #STR77##                             17                                                                              9 #STR78##                                                                                             0 #STR79##                                                                                1 #STR80##                             18                                                                              9 #STR81##                                                                                             0 #STR82##                                                                                2 #STR83##                             19                                                                              9 #STR84##                                                                                             0 #STR85##                                                                                3 #STR86##                             20                                                                              9 #STR87##                                                                                             0 #STR88##                                                                                4 #STR89##                             __________________________________________________________________________     * Cr below room temperature S.sub.B 81.8 Iso                             

                                      TABLE 3                                     __________________________________________________________________________    7 #STR90##       (A.sub.1 --Z.sub.1).sub.p                                                          (A.sub.2 --Z.sub.2).sub.q                                                          A.sub.3 --Z.sub.3 --A.sub.4                                                               8 #STR91##                             __________________________________________________________________________    21                                                                              9 #STR92##                                                                                             0 #STR93##                                                                                1 #STR94##                             22                                                                              9 #STR95##                                                                                             0 #STR96##                                                                                2 #STR97##                             23                                                                              9 #STR98##                                                                                             0 #STR99##                                                                                3 #STR100##                            24                                                                              9 #STR101##                                                                                            0 #STR102##                                                                               4 #STR103##                            25                                                                              5 #STR104##                                                                                            0 #STR105##                                                                               1 #STR106##                            26                                                                              5 #STR107##                                                                                            0 #STR108##                                                                               2 #STR109##                            27                                                                              5 #STR110##                                                                                            0 #STR111##                                                                               3 #STR112##                            28                                                                              5 #STR113##                                                                                            0 #STR114##                                                                               4 #STR115##                            29                                                                              6 #STR116##                                                                                            0 #STR117##                                                                               1 #STR118##                            30                                                                              6 #STR119##                                                                                            0 #STR120##                                                                               2 #STR121##                            31                                                                              6 #STR122##                                                                                            0 #STR123##                                                                               3 #STR124##                            32                                                                              6 #STR125##                                                                                            0 #STR126##                                                                               4 #STR127##                            33                                                                              8 #STR128##                                                                                            0 #STR129##                                                                               1 #STR130##                            34                                                                              8 #STR131##                                                                                            0 #STR132##                                                                               2 #STR133##                            35                                                                              8 #STR134##                                                                                            0 #STR135##                                                                               3 #STR136##                            36                                                                              8 #STR137##                                                                                            0 #STR138##                                                                               4 #STR139##                            37                                                                              9 #STR140##                                                                                            0 #STR141##                                                                               1 #STR142##                            38                                                                              9 #STR143##                                                                                            0 #STR144##                                                                               2 #STR145##                            39                                                                              9 #STR146##                                                                                            0 #STR147##                                                                               3 #STR148##                            40                                                                              9 #STR149##                                                                                            0 #STR150##                                                                               4 #STR151##                            __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    7 #STR152##      (A.sub.1 --Z.sub.1).sub.p                                                          (A.sub.2 --Z.sub.2).sub.q                                                          A.sub.3 --Z.sub.3 --A.sub.4                                                                  8 #STR153##                         __________________________________________________________________________    41                                                                              9 #STR154##                                                                                            1 #STR155##                                                                                  1 #STR156##                         42                                                                              9 #STR157##                                                                                            1 #STR158##                                                                                  2 #STR159##                         43                                                                              9 #STR160##                                                                                            1 #STR161##                                                                                  3 #STR162##                         44                                                                              9 #STR163##                                                                                            1 #STR164##                                                                                  4 #STR165##                         45                                                                              5 #STR166##                                                                                            1 #STR167##                                                                                  1 #STR168##                         46                                                                              5 #STR169##                                                                                            1 #STR170##                                                                                  2 #STR171##                         47                                                                              5 #STR172##                                                                                            1 #STR173##                                                                                  3 #STR174##                         48                                                                              5 #STR175##                                                                                            1 #STR176##                                                                                  4 #STR177##                         49                                                                              6 #STR178##                                                                                            1 #STR179##                                                                                  1 #STR180##                         50                                                                              6 #STR181##                                                                                            1 #STR182##                                                                                  2 #STR183##                         51                                                                              6 #STR184##                                                                                            1 #STR185##                                                                                  3 #STR186##                         52                                                                              6 #STR187##                                                                                            1 #STR188##                                                                                  4 #STR189##                         53                                                                              8 #STR190##                                                                                            1 #STR191##                                                                                  1 #STR192##                         54                                                                              8 #STR193##                                                                                            1 #STR194##                                                                                  2 #STR195##                         55                                                                              8 #STR196##                                                                                            1 #STR197##                                                                                  3 #STR198##                         56                                                                              8 #STR199##                                                                                            1 #STR200##                                                                                  4 #STR201##                         57                                                                              9 #STR202##                                                                                            1 #STR203##                                                                                  1 #STR204##                         58                                                                              9 #STR205##                                                                                            1 #STR206##                                                                                  2 #STR207##                         59                                                                              9 #STR208##                                                                                            1 #STR209##                                                                                  3 #STR210##                         60                                                                              9 #STR211##                                                                                            1 #STR212##                                                                                  4 #STR213##                         61                                                                              9 #STR214##                                                                                       2 #STR215##                                                                        0 #STR216##                                                                                  1 #STR217##                         62                                                                              9 #STR218##                                                                                       2 #STR219##                                                                        0 #STR220##                                                                                  2 #STR221##                         63                                                                              9 #STR222##                                                                                       2 #STR223##                                                                        0 #STR224##                                                                                  3 #STR225##                         64                                                                              9 #STR226##                                                                                       2 #STR227##                                                                        0 #STR228##                                                                                  4 #STR229##                         65                                                                              5 #STR230##                                                                                       2 #STR231##                                                                        0 #STR232##                                                                                  1 #STR233##                         66                                                                              5 #STR234##                                                                                       2 #STR235##                                                                        0 #STR236##                                                                                  2 #STR237##                         67                                                                              5 #STR238##                                                                                       2 #STR239##                                                                        0 #STR240##                                                                                  3 #STR241##                         68                                                                              5 #STR242##                                                                                       2 #STR243##                                                                        0 #STR244##                                                                                  4 #STR245##                         69                                                                              6 #STR246##                                                                                       2 #STR247##                                                                        0 #STR248##                                                                                  1 #STR249##                         70                                                                              6 #STR250##                                                                                       2 #STR251##                                                                        0 #STR252##                                                                                  2 #STR253##                         71                                                                              6 #STR254##                                                                                       2 #STR255##                                                                        0 #STR256##                                                                                  3 #STR257##                         72                                                                              6 #STR258##                                                                                       2 #STR259##                                                                        0 #STR260##                                                                                  4 #STR261##                         73                                                                              8 #STR262##                                                                                       2 #STR263##                                                                        0 #STR264##                                                                                  1 #STR265##                         74                                                                              8 #STR266##                                                                                       2 #STR267##                                                                        0 #STR268##                                                                                  2 #STR269##                         75                                                                              8 #STR270##                                                                                       2 #STR271##                                                                        0 #STR272##                                                                                  3 #STR273##                         76                                                                              8 #STR274##                                                                                       2 #STR275##                                                                        0 #STR276##                                                                                  4 #STR277##                         77                                                                              9 #STR278##                                                                                       2 #STR279##                                                                        0 #STR280##                                                                                  1 #STR281##                         78                                                                              9 #STR282##                                                                                       2 #STR283##                                                                        0 #STR284##                                                                                  2 #STR285##                         79                                                                              9 #STR286##                                                                                       2 #STR287##                                                                        0 #STR288##                                                                                  3 #STR289##                         80                                                                              9 #STR290##                                                                                       2 #STR291##                                                                        0 #STR292##                                                                                  4 #STR293##                         __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________    7 #STR294##       (A.sub.1 --Z.sub.1).sub.p                                                          (A.sub.2 --Z.sub.2).sub.q                                                           A.sub.3 --Z.sub.3 --A.sub.4                                                               8 #STR295##                          __________________________________________________________________________    81                                                                               9 #STR296##                                                                                       2 #STR297##                                                                         3 #STR298##                                                                               1 #STR299##                          82                                                                               9 #STR300##                                                                                       2 #STR301##                                                                         3 #STR302##                                                                               2 #STR303##                          83                                                                               9 #STR304##                                                                                       2 #STR305##                                                                         3 #STR306##                                                                               3 #STR307##                          84                                                                               9 #STR308##                                                                                       2 #STR309##                                                                         3 #STR310##                                                                               4 #STR311##                          85                                                                               5 #STR312##                                                                                       2 #STR313##                                                                         3 #STR314##                                                                               1 #STR315##                          86                                                                               5 #STR316##                                                                                       2 #STR317##                                                                         3 #STR318##                                                                               2 #STR319##                          87                                                                               5 #STR320##                                                                                       2 #STR321##                                                                         3 #STR322##                                                                               3 #STR323##                          88                                                                               5 #STR324##                                                                                       2 #STR325##                                                                         3 #STR326##                                                                               4 #STR327##                          89                                                                               6 #STR328##                                                                                       2 #STR329##                                                                         3 #STR330##                                                                               1 #STR331##                          90                                                                               6 #STR332##                                                                                       2 #STR333##                                                                         3 #STR334##                                                                               2 #STR335##                          91                                                                               6 #STR336##                                                                                       2 #STR337##                                                                         3 #STR338##                                                                               3 #STR339##                          92                                                                               6 #STR340##                                                                                       2 #STR341##                                                                         3 #STR342##                                                                               4 #STR343##                          93                                                                               8 #STR344##                                                                                       2 #STR345##                                                                         3 #STR346##                                                                               1 #STR347##                          94                                                                               8 #STR348##                                                                                       2 #STR349##                                                                         3 #STR350##                                                                               2 #STR351##                          95                                                                               8 #STR352##                                                                                       2 #STR353##                                                                         3 #STR354##                                                                               3 #STR355##                          96                                                                               8 #STR356##                                                                                       2 #STR357##                                                                         3 #STR358##                                                                               4 #STR359##                          97                                                                               9 #STR360##                                                                                       2 #STR361##                                                                         3 #STR362##                                                                               1 #STR363##                          98                                                                               9 #STR364##                                                                                       2 #STR365##                                                                         3 #STR366##                                                                               2 #STR367##                          99                                                                               9 #STR368##                                                                                       2 #STR369##                                                                         3 #STR370##                                                                               3 #STR371##                          100                                                                              9 #STR372##                                                                                       2 #STR373##                                                                         3 #STR374##                                                                               4 #STR375##                          __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________    7 #STR376##       (A.sub.1 --Z.sub.1).sub.p                                                          (A.sub.2 --Z.sub.2).sub.q                                                           A.sub.3 --Z.sub.3 --A.sub.4                                                               8 #STR377##                          __________________________________________________________________________    101                                                                              9 #STR378##                                                                                       2 #STR379##                                                                         4 #STR380##                                                                               1 #STR381##                          102                                                                              9 #STR382##                                                                                       2 #STR383##                                                                         4 #STR384##                                                                               2 #STR385##                          103                                                                              9 #STR386##                                                                                       2 #STR387##                                                                         4 #STR388##                                                                               3 #STR389##                          104                                                                              9 #STR390##                                                                                       2 #STR391##                                                                         4 #STR392##                                                                               4 #STR393##                          105                                                                              5 #STR394##                                                                                       2 #STR395##                                                                         4 #STR396##                                                                               1 #STR397##                          106                                                                              5 #STR398##                                                                                       2 #STR399##                                                                         4 #STR400##                                                                               2 #STR401##                          107                                                                              5 #STR402##                                                                                       2 #STR403##                                                                         4 #STR404##                                                                               3 #STR405##                          108                                                                              5 #STR406##                                                                                       2 #STR407##                                                                         4 #STR408##                                                                               4 #STR409##                          109                                                                              6 #STR410##                                                                                       2 #STR411##                                                                         4 #STR412##                                                                               1 #STR413##                          110                                                                              6 #STR414##                                                                                       2 #STR415##                                                                         4 #STR416##                                                                               2 #STR417##                          111                                                                              6 #STR418##                                                                                       2 #STR419##                                                                         4 #STR420##                                                                               3 #STR421##                          112                                                                              6 #STR422##                                                                                       2 #STR423##                                                                         4 #STR424##                                                                               4 #STR425##                          113                                                                              8 #STR426##                                                                                       2 #STR427##                                                                         4 #STR428##                                                                               1 #STR429##                          114                                                                              8 #STR430##                                                                                       2 #STR431##                                                                         4 #STR432##                                                                               2 #STR433##                          115                                                                              8 #STR434##                                                                                       2 #STR435##                                                                         4 #STR436##                                                                               3 #STR437##                          116                                                                              8 #STR438##                                                                                       2 #STR439##                                                                         4 #STR440##                                                                               4 #STR441##                          117                                                                              9 #STR442##                                                                                       2 #STR443##                                                                         4 #STR444##                                                                               1 #STR445##                          118                                                                              9 #STR446##                                                                                       2 #STR447##                                                                         4 #STR448##                                                                               2 #STR449##                          119                                                                              9 #STR450##                                                                                       2 #STR451##                                                                         4 #STR452##                                                                               3 #STR453##                          120                                                                              9 #STR454##                                                                                       2 #STR455##                                                                         4 #STR456##                                                                               4 #STR457##                          __________________________________________________________________________

                                      TABLE 8                                     __________________________________________________________________________    7 #STR458##       (A.sub.1 --Z.sub.1).sub.p                                                          (A.sub.2 --Z.sub.2).sub.q                                                                 A.sub.3 --Z.sub.3 --A.sub.4                                                                8 #STR459##                   __________________________________________________________________________    121                                                                              9 #STR460##                                                                                       5 #STR461##                                                                               0 #STR462##                                                                                1 #STR463##                   122                                                                              9 #STR464##                                                                                       5 #STR465##                                                                               0 #STR466##                                                                                2 #STR467##                   123                                                                              9 #STR468##                                                                                       5 #STR469##                                                                               0 #STR470##                                                                                3 #STR471##                   124                                                                              9 #STR472##                                                                                       5 #STR473##                                                                               0 #STR474##                                                                                4 #STR475##                   125                                                                              5 #STR476##                                                                                       5 #STR477##                                                                               0 #STR478##                                                                                1 #STR479##                   126                                                                              5 #STR480##                                                                                       5 #STR481##                                                                               0 #STR482##                                                                                2 #STR483##                   127                                                                              5 #STR484##                                                                                       5 #STR485##                                                                               0 #STR486##                                                                                3 #STR487##                   128                                                                              5 #STR488##                                                                                       5 #STR489##                                                                               0 #STR490##                                                                                4 #STR491##                   129                                                                              6 #STR492##                                                                                       5 #STR493##                                                                               0 #STR494##                                                                                1 #STR495##                   130                                                                              6 #STR496##                                                                                       5 #STR497##                                                                               0 #STR498##                                                                                2 #STR499##                   131                                                                              6 #STR500##                                                                                       5 #STR501##                                                                               0 #STR502##                                                                                3 #STR503##                   132                                                                              6 #STR504##                                                                                       5 #STR505##                                                                               0 #STR506##                                                                                4 #STR507##                   133                                                                              8 #STR508##                                                                                       5 #STR509##                                                                               0 #STR510##                                                                                1 #STR511##                   134                                                                              8 #STR512##                                                                                       5 #STR513##                                                                               0 #STR514##                                                                                2 #STR515##                   135                                                                              8 #STR516##                                                                                       5 #STR517##                                                                               0 #STR518##                                                                                3 #STR519##                   136                                                                              8 #STR520##                                                                                       5 #STR521##                                                                               0 #STR522##                                                                                4 #STR523##                   137                                                                              9 #STR524##                                                                                       5 #STR525##                                                                               0 #STR526##                                                                                1 #STR527##                   138                                                                              9 #STR528##                                                                                       5 #STR529##                                                                               0 #STR530##                                                                                2 #STR531##                   139                                                                              9 #STR532##                                                                                       5 #STR533##                                                                               0 #STR534##                                                                                3 #STR535##                   140                                                                              9 #STR536##                                                                                       5 #STR537##                                                                               0 #STR538##                                                                                4 #STR539##                   __________________________________________________________________________

                                      TABLE 9                                     __________________________________________________________________________    7 #STR540##       (A.sub.1 --Z.sub.1).sub.p                                                          (A.sub.2 --Z.sub.2).sub.q                                                                 A.sub.3 --Z.sub.3 --A.sub.4                                                                8 #STR541##                   __________________________________________________________________________    141                                                                              9 #STR542##                                                                                       5 #STR543##                                                                               3 #STR544##                                                                                1 #STR545##                   142                                                                              9 #STR546##                                                                                       5 #STR547##                                                                               3 #STR548##                                                                                2 #STR549##                   143                                                                              9 #STR550##                                                                                       5 #STR551##                                                                               3 #STR552##                                                                                3 #STR553##                   144                                                                              9 #STR554##                                                                                       5 #STR555##                                                                               3 #STR556##                                                                                4 #STR557##                   145                                                                              5 #STR558##                                                                                       5 #STR559##                                                                               3 #STR560##                                                                                1 #STR561##                   146                                                                              5 #STR562##                                                                                       5 #STR563##                                                                               3 #STR564##                                                                                2 #STR565##                   147                                                                              5 #STR566##                                                                                       5 #STR567##                                                                               3 #STR568##                                                                                3 #STR569##                   148                                                                              5 #STR570##                                                                                       5 #STR571##                                                                               0 #STR572##                                                                                4 #STR573##                   149                                                                              6 #STR574##                                                                                       5 #STR575##                                                                               0 #STR576##                                                                                1 #STR577##                   150                                                                              6 #STR578##                                                                                       5 #STR579##                                                                               0 #STR580##                                                                                2 #STR581##                   151                                                                              6 #STR582##                                                                                       5 #STR583##                                                                               0 #STR584##                                                                                3 #STR585##                   152                                                                              6 #STR586##                                                                                       5 #STR587##                                                                               0 #STR588##                                                                                4 #STR589##                   153                                                                              8 #STR590##                                                                                       5 #STR591##                                                                               0 #STR592##                                                                                1 #STR593##                   154                                                                              8 #STR594##                                                                                       5 #STR595##                                                                               0 #STR596##                                                                                2 #STR597##                   155                                                                              8 #STR598##                                                                                       5 #STR599##                                                                               0 #STR600##                                                                                3 #STR601##                   156                                                                              8 #STR602##                                                                                       5 #STR603##                                                                               0 #STR604##                                                                                4 #STR605##                   157                                                                              9 #STR606##                                                                                       5 #STR607##                                                                               0 #STR608##                                                                                1 #STR609##                   158                                                                              9 #STR610##                                                                                       5 #STR611##                                                                               0 #STR612##                                                                                2 #STR613##                   159                                                                              9 #STR614##                                                                                       5 #STR615##                                                                               0 #STR616##                                                                                3 #STR617##                   160                                                                              9 #STR618##                                                                                       5 #STR619##                                                                               0 #STR620##                                                                                4 #STR621##                   __________________________________________________________________________

                                      TABLE 10                                    __________________________________________________________________________    7 #STR622##       (A.sub.1 --Z.sub.1).sub.p                                                           (A.sub.2 --Z.sub.2).sub.q                                                           A.sub.3 --Z.sub.3 --A.sub.4                                                               8 #STR623##                         __________________________________________________________________________    161                                                                              9 #STR624##                                                                                  2 #STR625##                                                                         2 #STR626##                                                                         3 #STR627##                                                                               1 #STR628##                         162                                                                              9 #STR629##                                                                                  2 #STR630##                                                                         2 #STR631##                                                                         3 #STR632##                                                                               2 #STR633##                         163                                                                              9 #STR634##                                                                                  2 #STR635##                                                                         2 #STR636##                                                                         3 #STR637##                                                                               3 #STR638##                         164                                                                              9 #STR639##                                                                                  2 #STR640##                                                                         2 #STR641##                                                                         3 #STR642##                                                                               4 #STR643##                         165                                                                              5 #STR644##                                                                                  2 #STR645##                                                                         2 #STR646##                                                                         3 #STR647##                                                                               1 #STR648##                         166                                                                              5 #STR649##                                                                                  2 #STR650##                                                                         2 #STR651##                                                                         3 #STR652##                                                                               2 #STR653##                         167                                                                              5 #STR654##                                                                                  2 #STR655##                                                                         2 #STR656##                                                                         3 #STR657##                                                                               3 #STR658##                         168                                                                              5 #STR659##                                                                                  2 #STR660##                                                                         2 #STR661##                                                                         3 #STR662##                                                                               4 #STR663##                         169                                                                              6 #STR664##                                                                                  2 #STR665##                                                                         2 #STR666##                                                                         3 #STR667##                                                                               1 #STR668##                         170                                                                              6 #STR669##                                                                                  2 #STR670##                                                                         2 #STR671##                                                                         3 #STR672##                                                                               2 #STR673##                         171                                                                              6 #STR674##                                                                                  2 #STR675##                                                                         2 #STR676##                                                                         3 #STR677##                                                                               3 #STR678##                         172                                                                              6 #STR679##                                                                                  2 #STR680##                                                                         2 #STR681##                                                                         3 #STR682##                                                                               4 #STR683##                         173                                                                              8 #STR684##                                                                                  2 #STR685##                                                                         2 #STR686##                                                                         3 #STR687##                                                                               1 #STR688##                         174                                                                              8 #STR689##                                                                                  2 #STR690##                                                                         2 #STR691##                                                                         3 #STR692##                                                                               2 #STR693##                         175                                                                              8 #STR694##                                                                                  2 #STR695##                                                                         2 #STR696##                                                                         3 #STR697##                                                                               3 #STR698##                         176                                                                              8 #STR699##                                                                                  2 #STR700##                                                                         2 #STR701##                                                                         3 #STR702##                                                                               4 #STR703##                         177                                                                              9 #STR704##                                                                                  2 #STR705##                                                                         2 #STR706##                                                                         3 #STR707##                                                                               1 #STR708##                         178                                                                              9 #STR709##                                                                                  2 #STR710##                                                                         2 #STR711##                                                                         3 #STR712##                                                                               2 #STR713##                         179                                                                              9 #STR714##                                                                                  2 #STR715##                                                                         2 #STR716##                                                                         3 #STR717##                                                                               3 #STR718##                         180                                                                              9 #STR719##                                                                                  2 #STR720##                                                                         2 #STR721##                                                                         3 #STR722##                                                                               4 #STR723##                         __________________________________________________________________________

                                      TABLE 11                                    __________________________________________________________________________    1 #STR724##       (A.sub.1 --Z.sub.1).sub.p                                                           (A.sub.2 --Z.sub.2).sub.q                                                           A.sub.3 --Z.sub.3 --A.sub.4                                                               2 #STR725##                         __________________________________________________________________________    181                                                                              3 #STR726##                                                                                  4 #STR727##                                                                         5 #STR728##                                                                         6 #STR729##                                                                               7 #STR730##                         182                                                                              3 #STR731##                                                                                  4 #STR732##                                                                         5 #STR733##                                                                         6 #STR734##                                                                               8 #STR735##                         183                                                                              3 #STR736##                                                                                  4 #STR737##                                                                         5 #STR738##                                                                         6 #STR739##                                                                               9 #STR740##                         184                                                                              3 #STR741##                                                                                  4 #STR742##                                                                         5 #STR743##                                                                         6 #STR744##                                                                               0 #STR745##                         185                                                                              1 #STR746##                                                                                  4 #STR747##                                                                         5 #STR748##                                                                         6 #STR749##                                                                               7 #STR750##                         186                                                                              1 #STR751##                                                                                  4 #STR752##                                                                         5 #STR753##                                                                         6 #STR754##                                                                               2 #STR755##                         187                                                                              1 #STR756##                                                                                  4 #STR757##                                                                         5 #STR758##                                                                         6 #STR759##                                                                               9 #STR760##                         188                                                                              1 #STR761##                                                                                  4 #STR762##                                                                         5 #STR763##                                                                         6 #STR764##                                                                               0 #STR765##                         189                                                                              3 #STR766##                                                                                  4 #STR767##                                                                         5 #STR768##                                                                         6 #STR769##                                                                               7 #STR770##                         190                                                                              3 #STR771##                                                                                  4 #STR772##                                                                         5 #STR773##                                                                         6 #STR774##                                                                               8 #STR775##                         191                                                                              3 #STR776##                                                                                  4 #STR777##                                                                         5 #STR778##                                                                         6 #STR779##                                                                               9 #STR780##                         192                                                                              3 #STR781##                                                                                  4 #STR782##                                                                         5 #STR783##                                                                         6 #STR784##                                                                               0 #STR785##                         193                                                                              4 #STR786##                                                                                  4 #STR787##                                                                         5 #STR788##                                                                         6 #STR789##                                                                               7 #STR790##                         194                                                                              4 #STR791##                                                                                  4 #STR792##                                                                         5 #STR793##                                                                         6 #STR794##                                                                               8 #STR795##                         195                                                                              4 #STR796##                                                                                  4 #STR797##                                                                         5 #STR798##                                                                         6 #STR799##                                                                               9 #STR800##                         196                                                                              4 #STR801##                                                                                  4 #STR802##                                                                         5 #STR803##                                                                         6 #STR804##                                                                               0 #STR805##                         197                                                                              5 #STR806##                                                                                  4 #STR807##                                                                         5 #STR808##                                                                         6 #STR809##                                                                               7 #STR810##                         198                                                                              5 #STR811##                                                                                  4 #STR812##                                                                         5 #STR813##                                                                         6 #STR814##                                                                               8 #STR815##                         199                                                                              5 #STR816##                                                                                  4 #STR817##                                                                         5 #STR818##                                                                         6 #STR819##                                                                               9 #STR820##                         200                                                                              5 #STR821##                                                                                  4 #STR822##                                                                         5 #STR823##                                                                         6 #STR824##                                                                               0 #STR825##                         __________________________________________________________________________

                                      TABLE 12                                    __________________________________________________________________________    1 #STR826##       (A.sub.1 --Z.sub.1).sub.p                                                           (A.sub.2 --Z.sub.2).sub.q                                                           A.sub.3 --Z.sub.3 --A.sub.4                                                               2 #STR827##                         __________________________________________________________________________    201                                                                              3 #STR828##                                                                                  4 #STR829##                                                                         8 #STR830##                                                                         6 #STR831##                                                                               7 #STR832##                         202                                                                              3 #STR833##                                                                                  4 #STR834##                                                                         8 #STR835##                                                                         6 #STR836##                                                                               8 #STR837##                         203                                                                              3 #STR838##                                                                                  4 #STR839##                                                                         8 #STR840##                                                                         6 #STR841##                                                                               9 #STR842##                         204                                                                              3 #STR843##                                                                                  4 #STR844##                                                                         8 #STR845##                                                                         6 #STR846##                                                                               0 #STR847##                         205                                                                              1 #STR848##                                                                                  4 #STR849##                                                                         8 #STR850##                                                                         6 #STR851##                                                                               7 #STR852##                         206                                                                              1 #STR853##                                                                                  4 #STR854##                                                                         8 #STR855##                                                                         6 #STR856##                                                                               8 #STR857##                         207                                                                              1 #STR858##                                                                                  4 #STR859##                                                                         8 #STR860##                                                                         6 #STR861##                                                                               9 #STR862##                         208                                                                              1 #STR863##                                                                                  4 #STR864##                                                                         8 #STR865##                                                                         6 #STR866##                                                                               0 #STR867##                         209                                                                              3 #STR868##                                                                                  4 #STR869##                                                                         8 #STR870##                                                                         6 #STR871##                                                                               7 #STR872##                         210                                                                              3 #STR873##                                                                                  4 #STR874##                                                                         8 #STR875##                                                                         6 #STR876##                                                                               8 #STR877##                         211                                                                              3 #STR878##                                                                                  4 #STR879##                                                                         8 #STR880##                                                                         6 #STR881##                                                                               9 #STR882##                         212                                                                              3 #STR883##                                                                                  4 #STR884##                                                                         8 #STR885##                                                                         6 #STR886##                                                                               0 #STR887##                         213                                                                              4 #STR888##                                                                                  4 #STR889##                                                                         8 #STR890##                                                                         6 #STR891##                                                                               7 #STR892##                         214                                                                              4 #STR893##                                                                                  4 #STR894##                                                                         8 #STR895##                                                                         6 #STR896##                                                                               8 #STR897##                         215                                                                              4 #STR898##                                                                                  4 #STR899##                                                                         8 #STR900##                                                                         6 #STR901##                                                                               9 #STR902##                         216                                                                              4 #STR903##                                                                                  4 #STR904##                                                                         8 #STR905##                                                                         6 #STR906##                                                                               0 #STR907##                         217                                                                              5 #STR908##                                                                                  4 #STR909##                                                                         8 #STR910##                                                                         6 #STR911##                                                                               7 #STR912##                         218                                                                              5 #STR913##                                                                                  4 #STR914##                                                                         8 #STR915##                                                                         6 #STR916##                                                                               8 #STR917##                         219                                                                              5 #STR918##                                                                                  4 #STR919##                                                                         8 #STR920##                                                                         6 #STR921##                                                                               9 #STR922##                         220                                                                              5 #STR923##                                                                                  4 #STR924##                                                                         8 #STR925##                                                                         6 #STR926##                                                                               0 #STR927##                         __________________________________________________________________________

                                      TABLE 13                                    __________________________________________________________________________    1 #STR928##       (A.sub.1 --Z.sub.1).sub.p                                                           (A.sub.2 --Z.sub.2).sub.q                                                           A.sub.3 --Z.sub.3 --A.sub.4                                                               2 #STR929##                         __________________________________________________________________________    221                                                                              3 #STR930##                                                                                  7 #STR931##                                                                         8 #STR932##                                                                         6 #STR933##                                                                               7 #STR934##                         222                                                                              3 #STR935##                                                                                  7 #STR936##                                                                         8 #STR937##                                                                         6 #STR938##                                                                               8 #STR939##                         223                                                                              3 #STR940##                                                                                  7 #STR941##                                                                         8 #STR942##                                                                         6 #STR943##                                                                               9 #STR944##                         224                                                                              3 #STR945##                                                                                  7 #STR946##                                                                         8 #STR947##                                                                         6 #STR948##                                                                               0 #STR949##                         225                                                                              1 #STR950##                                                                                  7 #STR951##                                                                         8 #STR952##                                                                         6 #STR953##                                                                               7 #STR954##                         226                                                                              1 #STR955##                                                                                  7 #STR956##                                                                         8 #STR957##                                                                         6 #STR958##                                                                               8 #STR959##                         227                                                                              1 #STR960##                                                                                  7 #STR961##                                                                         8 #STR962##                                                                         6 #STR963##                                                                               9 #STR964##                         228                                                                              1 #STR965##                                                                                  7 #STR966##                                                                         8 #STR967##                                                                         6 #STR968##                                                                               0 #STR969##                         229                                                                              3 #STR970##                                                                                  7 #STR971##                                                                         8 #STR972##                                                                         6 #STR973##                                                                               7 #STR974##                         230                                                                              3 #STR975##                                                                                  7 #STR976##                                                                         8 #STR977##                                                                         6 #STR978##                                                                               8 #STR979##                         231                                                                              3 #STR980##                                                                                  7 #STR981##                                                                         8 #STR982##                                                                         6 #STR983##                                                                               9 #STR984##                         232                                                                              3 #STR985##                                                                                  7 #STR986##                                                                         8 #STR987##                                                                         6 #STR988##                                                                               0 #STR989##                         233                                                                              4 #STR990##                                                                                  7 #STR991##                                                                         8 #STR992##                                                                         6 #STR993##                                                                               7 #STR994##                         234                                                                              4 #STR995##                                                                                  7 #STR996##                                                                         8 #STR997##                                                                         6 #STR998##                                                                               8 #STR999##                         235                                                                              4 #STR1000##                                                                                 7 #STR1001##                                                                        8 #STR1002##                                                                        6 #STR1003##                                                                              9 #STR1004##                        236                                                                              4 #STR1005##                                                                                 7 #STR1006##                                                                        8 #STR1007##                                                                        6 #STR1008##                                                                              0 #STR1009##                        237                                                                              5 #STR1010##                                                                                 7 #STR1011##                                                                        8 #STR1012##                                                                        6 #STR1013##                                                                              7 #STR1014##                        238                                                                              5 #STR1015##                                                                                 7 #STR1016##                                                                        8 #STR1017##                                                                        6 #STR1018##                                                                              8 #STR1019##                        239                                                                              5 #STR1020##                                                                                 7 #STR1021##                                                                        8 #STR1022##                                                                        6 #STR1023##                                                                              9 #STR1024##                        240                                                                              5 #STR1025##                                                                                 7 #STR1026##                                                                        8 #STR1027##                                                                        6 #STR1028##                                                                              0 #STR1029##                        __________________________________________________________________________

                                      TABLE 14                                    __________________________________________________________________________    1 #STR1030##      (A.sub.1 --Z.sub.1).sub.p                                                                 (A.sub.2 --Z.sub.2).sub.q                                                           A.sub.3 --Z.sub.3 --A.sub.4                                                               2 #STR1031##                  __________________________________________________________________________    241                                                                              3 #STR1032##                                                                                                   0 #STR1033##                                                                              3 #STR1034##                  242                                                                              3 #STR1035##                                                                                                   0 #STR1036##                                                                              4 #STR1037##                  243                                                                              1 #STR1038##                                                                                                   1 #STR1039##                                                                              5 #STR1040##                  244                                                                              3 #STR1041##                                                                                                   0 #STR1042##                                                                              6 #STR1043##                  245                                                                              1 #STR1044##                                                                                                   6 #STR1045##                                                                              7 #STR1046##                  246                                                                              3 #STR1047##                                                                                             4 #STR1048##                                                                        0 #STR1049##                                                                              3 #STR1050##                  247                                                                              1 #STR1051##                                                                                             4 #STR1052##                                                                        0 #STR1053##                                                                              4 #STR1054##                  248                                                                              3 #STR1055##                                                                                             4 #STR1056##                                                                        6 #STR1057##                                                                              5 #STR1058##                  249                                                                              4 #STR1059##                                                                                             8 #STR1060##                                                                        0 #STR1061##                                                                              8 #STR1062##                  250                                                                              3 #STR1063##                                                                                             4 #STR1064##                                                                        2 #STR1065##                                                                              4 #STR1066##                  251                                                                              1 #STR1067##                                                                                             4 #STR1068##                                                                        2 #STR1069##                                                                              6 #STR1070##                  252                                                                              3 #STR1071##                                                                                             8 #STR1072##                                                                        6 #STR1073##                                                                              7 #STR1074##                  253                                                                              3 #STR1075##                                                                                 4 #STR1076##                                                                              4 #STR1077##                                                                        0 #STR1078##                                                                              4 #STR1079##                  254                                                                              1 #STR1080##                                                                                 4 #STR1081##                                                                              4 #STR1082##                                                                        0 #STR1083##                                                                              5 #STR1084##                  255                                                                              3 #STR1085##                                                                                 9 #STR1086##                                                                              4 #STR1087##                                                                        6 #STR1088##                                                                              8 #STR1089##                  256                                                                              3 #STR1090##                                                                                 8 #STR1091##                                                                              8 #STR1092##                                                                        2 #STR1093##                                                                              8 #STR1094##                  257                                                                              4 #STR1095##                                                                                 8 #STR1096##                                                                              8 #STR1097##                                                                        6 #STR1098##                                                                              4 #STR1099##                  258                                                                              3 #STR1100##                                                                                 4 #STR1101##                                                                              8 #STR1102##                                                                        2 #STR1103##                                                                              3 #STR1104##                  259                                                                              1 #STR1105##                                                                                 4 #STR1106##                                                                              8 #STR1107##                                                                        2 #STR1108##                                                                              4 #STR1109##                  260                                                                              5 #STR1110##                                                                                 8 #STR1111##                                                                              4 #STR1112##                                                                        6 #STR1113##                                                                              6 #STR1114##                  261                                                                              1 #STR1115##                                                                                 8 #STR1116##                                                                              4 #STR1117##                                                                        0 #STR1118##                                                                              8 #STR1119##                  262                                                                              4 #STR1120##                                                                                 4 #STR1121##                                                                              8 #STR1122##                                                                        0 #STR1123##                                                                              5 #STR1124##                  __________________________________________________________________________

EXAMPLE 4

(Use Example 1)

Liquid crystal composition (mother liquid crystal) comprising

    ______________________________________                                        4-(trans-4-propylcyclohexyl)benzonitrile                                                           30% by weight                                            4-(trans-4-pentylcyclohexyl)benzonitrile                                                           40% by weight                                            4-(trans-4-heptylcyclohexyl)benzonitrile                                                           30% by weight                                            ______________________________________                                    

was prepared. This composition had a clearing point (Cp.) of 52.3° C.,Δε of 10.7, Δn of 0.119, viscosity at 20° C. (η₂₀) of 21.4 mPa·s, andVth when filled in a TN cell of 9 μm thickness of 1.60 V.

When a liquid crystal composition was prepared by mixing 15 parts byweight of the compound of the present invention,1-(3-butenyl)-trans-4-(trans-4-((E)-(5-fluoro-1-pentenyl)cyclohexyl)cyclohexane (Compound No. 11), obtained in Example 1 with 85 parts byweight of the mother liquid crystal described above, the compositionthus obtained had a Cp. of 54.2° C., V_(th) of 1.61 V, Δε of 9.3, Δn of0.109, η₂₀ of 19.0 mPa·s, K₃₃ /K₁ l of 2.23, and Vth when filled in a TNcell of 9 μm thickness of 1.61 V. Whereas this liquid crystalcomposition was left in a freezer at -20° C. for 25 days, separation ofcrystals and development of a smectic phase were not observed.

Comparative Example

For comparison, a compound expressed by the formula (a) recited abovewherein R represents propyl group and alkenyl is 3-butenyl group wassynthesized, a liquid crystal composition was prepared in the samemanner as in Example 4 with the exception that the comparative compoundwas used in place of the compound (Compound No. 11), and then K₃₃ /K₁₁of the liquid crystal composition thus obtained was determined to findto be 1.78.

This value was clearly poor compared with that of 2.23 obtained when thecompound mentioned above (Compound No. 11) was used (as shown in Example4).

INDUSTRIAL APPLICABILITY

As described above, any compounds of the present invention areconsiderably excellent as liquid crystal compound particularly for STNdisplay mode, since they have a wide temperature range of a liquidcrystal phase, low viscosity, medium degree of Δε, and large K₃₃ /K₁₁,and they are readily mixed with various other liquid crystal materialseven at low temperatures.

Accordingly, when the compounds of the present invention are used ascomponent of liquid crystal compositions, novel liquid crystalcompositions which have desired physical properties in addition to acharacteristic of having an excellent mutual solubility with otherliquid crystal materials, can be provided by suitably selectingsix-membered rings, substituents and/or bonding groups of moleculeconstituting elements.

We claim:
 1. A fluoroalkenyl derivative expressed by the general formula(1) ##STR1125## wherein A₁, A₂, A₃, and A₄ independently representtrans-1,4-cyclohexylene group or 1,4-phenylene group at least onehydrogen atom on which six-membered ring may be replaced by a halogenatom; Z₁, Z₂, and Z₃ independently represent --(CH₂)₂ --, --CH═CH--,--C≡C--, or a single bond; Q represents H or F; l is an integer of 1 to5; m, n, and 0 are independently an integer of 0 to 5; p and q areindependently an integer of 0 or
 1. 2. The fluoroalkenyl derivativeaccording to claim 1 wherein Z₃ represents a single bond; both A₃ and A₄represent trans-1,4-cyclohexylene group; and both p and q are
 0. 3. Thefluoroalkenyl derivative according to claim 1 wherein both Z₂ and Z₃represent a single bond; A₂, A₃, and A₄ representtrans-1,4-cyclohexylene group; p is 0; and q is
 1. 4. The fluoroalkenylderivative according to claim 1 wherein both Z₂ and Z₃ represent asingle bond; both A₂ and A₄ represent trans-1,4-cyclohexylene group; A₃represents 1,4-phenylene group; p is 0; and q is
 1. 5. The fluoroalkenylderivative according to claim 1 wherein Z₁, Z₂, and Z₃ represent asingle bond; both A₁ and A₄ represent trans-1,4-cyclohexylene group;both A₂ and A₃ represent 1,4-phenylene group; and both p and q are
 1. 6.A liquid crystal composition comprising at least 2 components andcomprising at least one fluoroalkenyl derivative defined in any one ofclaims 1 to
 5. 7. A liquid crystal composition comprising, as a firstcomponent, at least one fluoroalkenyl derivative defined in any one ofclaims 1 to 5, and comprising, as a second component, at least onecompound selected from the group consisting of the compounds expressedby any one of the general formulas (2), (3), and (4) ##STR1126## whereinR₁ represents an alkyl group having 1 to 10 carbon atoms; X₁ representsF, Cl, OCF₃, OCF₂ H, CF₃, CF₂ H, or CFH₂ ; L₁, L₂, L₃, and L₄independently represent H or F; Z₄ and Z₅ independently represent--(CH₂)₂ --, --CH═CH--, or a covalent bond; and a is 1 or
 2. 8. A liquidcrystal display device comprising a liquid crystal composition definedin claim
 6. 9. A liquid crystal display device comprising a liquidcrystal composition defined in claim
 7. 10. A liquid crystal compositioncomprising, as a first component, at least one fluoroalkenyl derivativedefined in any one of claims 1 to 5, and as a second component, at leastone compound selected from the group consisting of the compoundsexpressed by any one of the general formulas (5), (6), (7), (8) and (9)##STR1127## wherein R₂ represents F, an alkyl group having 1 to 10carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, in whichalkyl group or alkenyl group one or more non-adjacent methylene groups(--CH₂ --) may each be replaced by an oxygen atom (--O--); ring Arepresents trans-1,4-cyclohexylene group, 1,4-phenylene group,pyrimidine-2,5-diyl group, or 1,3-dioxane-2,5-diyl group; ring Brepresents trans-1,4-cyclohexylene group, 1,4-phenylene group, orpyrimidine-2,5-diyl group; ring C represents trans-1,4-cyclohexylenegroup or 1,4-phenylene group; Z₆ represents --(CH₂)₂ --, --COO--, or asingle bond; L₅ and L₆ independently represent H or F; and b and c areindependently 0 or 1, ##STR1128## wherein R₃ represents an alkyl grouphaving 1 to 10 carbon atoms; L₇ represents H or F; and d is 0 or 1,##STR1129## wherein R₄ represents an alkyl group having 1 to 10 carbonatoms; ring D and ring E independently represent trans-1,4-cyclohexylenegroup or 1,4-phenylene group; Z₇ and Z₈ independently represent --COO--or a single bond; Z₉ represents --COO-- or --C≡C--; L₈ and L₉independently represent H or F; X₂ represents F, OCF₃, OCF₂ H, CF₃, CF₂H, or CFH₂ ; and e, f, and g are independently 0 or 1, ##STR1130##wherein R₅ and R₆ independently represent an alkyl group having 1 to 10carbon atoms or an alkenyl group having 2 to 10 carbon atoms, in whichalkyl or alkenyl group one or more non-adjacent methylene groups (--CH₂--) may each be replaced by an oxygen atom (--O--) ; ring G representstrans-1, 4-cyclohexylene group, 1, 4-phenylene group, orpyrimidine-2,5-diyl group; ring H represents trans-1,4-cyclohexylenegroup or 1,4-phenylene group; Z₁₀ represents --C≡C--, --COO--, --(CH₂)₂--, --CH═CH--C≡C--, or a single bond; and Z₁₁ represents --COO-- or asingle bond, ##STR1131## wherein R₇ and R₈ independently represent analkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to10 carbon atoms, in which alkyl or alkenyl group one or morenon-adjacent methylene groups (--CH₂ --) may each be replaced by anoxygen atom (--O--); ring I represents trans-1,4-cyclohexylene group,1,4-phenylene group, or pyrimidine-2,5-diyl group; ring J representstrans-1,4-cyclohexylene group, 1,4-phenylene group at least one hydrogenatom on which ring may be replaced by F, or pyrimidine-2,5-diyl group;ring K represents trans-1,4-cyclohexylene group or 1,4-phenylene group;Z₁₂ and Z₁₄ independently represent --COO--, --(CH₂)₂ --, or a singlebond; Z₁₃ represents --CH═CH--, --C≡C--, --COO--, or a single bond; andh is 0 or
 1. 11. A liquid crystal composition comprising, as a firstcomponent, at least one fluoroalkenyl derivative defined in any one ofclaims 1 to 5, as a part of a second component, at least one compoundselected from the group consisting of the compounds expressed by any oneof the general formulas (2), (3) and (4), and as another part of thesecond component, at least one compound selected from the groupconsisting of the compounds expressed by any one of the general formulas(5), (6), (7), (8) and (9), ##STR1132## wherein R₁ represents an alkylgroup having 1 to 10 carbon atoms; X₁ represents F, Cl, OCF₃, OCF₂ H,CF₃, CF₂ H, or CFH₂ ; L₁, L₂, L₃, and L₄ independently represent H or F;Z₄ and Z₅ independently represent --(CH₂)₂ --, --CH═CH--, or a singlebond; and a is 1 or 2, ##STR1133## wherein R₂ represents F, an alkylgroup having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10carbon atoms, in which alkyl group or alkenyl group one or morenon-adjacent methylene groups (--CH₂ --) may each be replaced by anoxygen atom (--O--); ring A represents trans-1,4-cyclohexylene group,1,4-phenylene group, pyrimidine-2,5-diyl group, or 1,3-dioxane-2,5-diylgroup; ring B represents trans-1,4-cyclohexylene group, 1,4-phenylenegroup, or pyrimidine-2,5-diyl group; ring C representstrans-1,4-cyclohexylene group or 1, 4-phenylene group; Z₆ represents--(CH₂)₂ --, --COO--, or a single bond; L₅ and L₆ independentlyrepresent H or F; and b and c are independently 0 or 1, ##STR1134##wherein R₃ represents an alkyl group having 1 to 10 carbon atoms; L₇represents H or F; and d is 0 or 1, ##STR1135## wherein R₄ represents analkyl group having 1 to 10 carbon atoms; ring D and ring E independentlyrepresent trans-1,4-cyclohexylene group or 1,4-phenylene group; Z₇ andZ, independently represent --COO-- or a single bond; Z₉ represents--COO-- or --C≡C--; L₈ and L₉ independently represent H or F; X₂represents F, OCF₃, OCF₂ H, CF₃, CF₂ H, or CFH₂ ; and e, f, and g areindependently 0 or 1, ##STR1136## wherein R₅ and R₆ independentlyrepresent an alkyl group having 1 to 10 carbon atoms or an alkenyl grouphaving 2 to 10 carbon atoms, in which alkyl or alkenyl group one or morenon-adjacent methylene groups (--CH₂ --) may each be replaced by anoxygen atom (--O--); ring G represents trans-1,4-cyclohexylene group,1,4-phenylene group, or pyrimidine-2,5-diyl group; ring H representstrans-1,4-cyclohexylene group or 1,4-phenylene group; Z₁₀ represents--C≡C--, --COO--, --(CH₂)₂ --, --CH═CH--C≡C--, or a single bond; and Z₁₁represents --COO-- or a single bond, and Z₁₁ represents --COO-- or asingle bond, ##STR1137## wherein R₇ and R₈ independently represent analkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to10 carbon atoms, in which alkyl or alkenyl group one or morenon-adjacent methylene groups (--CH₂ --) may each be replaced by anoxygen atom (--O--); ring I represents trans-1,4-cyclohexylene group,1,4-phenylene group, or pyrimidine-2,5-diyl group; ring J representstrans-1,4-cyclohexylene group, 1,4-phenylene group at least one hydrogenatom on which ring may be replaced by F, or pyrimidine-2,5-diyl group;ring K represents trans-1,4-cyclohexylene group or 1,4-phenylene group;Z₁₂ and Z₁₄ independently represent --COO--, --(CH₂)₂ --, or a singlebond; Z₁₃ represents --CH═CH--, --C≡C--, --COO--, or a single bond; andh is 0 or
 1. 12. A liquid crystal display device comprising a liquidcrystal composition defined in claim
 10. 13. A liquid crystal displaydevice comprising a liquid crystal composition defined in claim 11.